Perfluoropolyether urethane additives having (meth)acryl groups and hard coats

ABSTRACT

Fluorocarbon- and urethane-(meth)acryl-containing additives and hardcoats. The hardcoats are particularly useful as a surface layer on an optical device.

RELATED APPLICATION DATA

This is a divisional of U.S. Ser. No. 13/908,102, filed Jun. 3, 2013(U.S. Pat. No. 8,729,211), which is a continuation of U.S. Ser. No.13/396,669, filed Feb. 15, 2012 (U.S. Pat. No. 8,476,398), which is adivisional of U.S. Ser. No. 12/718,481, filed Mar. 5, 2010 (U.S. Pat.No. 8,147,966), which is a divisional of U.S. Ser. No. 11/277,162, filedMar. 22, 2006 (U.S. Pat. No. 7,718,264), which is a continuation in partof U.S. Ser. No. 11/087,413, filed Mar. 23, 2005 (abandoned).

BACKGROUND OF THE INVENTION

Optical hard coats are applied to optical display surfaces to protectthem from scratching and marking. Desirable product features in opticalhard coats include durability to scratches and abrasions, and resistanceto inks and stains.

Materials that have been used to date for surface protection includefluorinated polymers, or fluoropolymers. Fluoropolymers provideadvantages over conventional hydrocarbon based materials in terms ofhigh chemical inertness (solvent, acid, and base resistance), dirt andstain resistance (due to low surface energy), low moisture absorption,and resistance to weather and solar conditions.

Fluoropolymers have also been investigated that are crosslinked to ahydrocarbon-based hard coating formulation that improves hardness andinterfacial adhesion to a substrate. For example, it is known thatfree-radically curable perfluoropolyethers provide good repellency toinks from pens and permanent markers when added to ceramer hard coatcompositions, which comprise a plurality of colloidal inorganic oxideparticles and a free-radically curable binder precursor, such asdescribed in U.S. Pat. No. 6,238,798 to Kang, and assigned to 3MInnovative Properties Company of St. Paul, Minn.

Industry would find advantage in other fluoropolymer-based hardcoatings, particularly those having improved properties.

SUMMARY OF THE INVENTION

In one aspect, the invention relates to fluorocarbon- andurethane-(meth)acryl-containing compositions suitable for use asadditives in surface layer compositions for optical displays and otheruses.

In one embodiment, the composition comprises a perfluoropolyetherurethane having a monovalent perfluoropolyether moiety and amulti-(meth)acryl terminal group and is described in the detaileddescription below as Formula (1).

In another embodiment, the composition comprises aperfluoropolyether-substituted urethane acrylate having a monovalentperfluoropolyether moiety described in the detailed description below asFormula (3A) and more preferably as Formula (3B).

In a third embodiment, the composition comprises one or moreperfluoropolyether urethanes having a monovalent perfluoropolyethermoiety and a multi-(meth)acryl group of the Formula (4) as describedfurther in the detailed description below.

In a fourth embodiment, the composition comprises one or moreperfluoropolyether urethanes having a monovalent perfluoropolyethermoiety and a multi-(meth)acryl group of the Formula (5) as describedbelow in the detailed description.

In a fifth embodiment, the composition comprises one or moreperfluoropolyether urethanes with multi-(meth)acryl groups of theFormula (6) as described below in the detailed description.

In other embodiments, polymerizable compositions, hardcoat composition,protective films and optical display are described having theperfluoropolyether urethanes of Formulas 1-6, a hydrocarbon hardcoatcomposition; and optionally a plurality of surface modified inorganicnanoparticles.

In other embodiments, articles such as optical displays and protectivefilms are described that comprise an optical substrate having a surfacelayer comprising the reaction product of a mixture comprising i) atleast one non-fluorinated crosslinking agent, and

ii) at least one perfluoropolyether urethane having a perfluoropolyethermoiety and at least one free-radically reactive group; and a hardcoatlayer comprising inorganic oxide particles disposed between thesubstrate and the surface layer.

The perfluoropolyether urethane additives can improve the compatibilityof other fluorinated components such as free-radically reactiveperfluoropolyether, fluoroalkyl, or fluoroalkylene group-containingcomponents, such as for example perfluorobutyl-substituted acrylatecomponents, as well as fluoroalkyl- or fluoroalkylene-substituted thiolor polythiol components.

In other embodiments, polymerizable coating compositions, hardcoatsurface layers, optical displays, and protective films are describedwherein the polymerizable composition comprises i) a hydrocarbon-basedhardcoat composition (e.g. a non-fluorinated crosslinking agent); ii) atleast one perfluoropolyether urethane having a perfluoropolyether moietyand at least one free-radically reactive group; iii) and at least onefluorinated compound having at least one moiety selected fromfluoropolyether, fluoroalkyl, and fluoroalkylene linked to at least onefree-radically reactive group with a non-urethane linking group.

In some aspects ii) comprises at least two (meth)acryl groups such as aterminal group having at least two (meth)acryl groups, with(meth)acrylates groups being preferred and acrylate groups being morepreferred. Both ii) and iii) may comprise the perfluoropolyether moietyF(CF(CF₃)CF₂O)_(a)CF(CF₃)— wherein a ranges from 4 to 15.

Fluorinated compound iii) may be a mono- or multi-(meth)acrylatefunctional (e.g. perfluoropolyether) compound. The polymerizablecomposition may have a total weight percent fluorine ranging from 0.5 to5 wt-%. The amount of i) may comprise at least about 75 wt-% of themixture. Further, ii) and iii) may be present at a ratio ranging from1:1 to 3:1. In one aspect, iii) has a ratio of fluorine atoms tonon-fluorine atoms that is higher than ii). In another aspect, iii) hasa lower molecular weight than ii).

Further, a particulate matting agent may be incorporated to impartanti-glare properties to the optical hard coating layer. The particulatematting agent can also prevent the reflectance decrease and unevencoloration caused by interference of the hard coat layer with theunderlying substrate layer. In preferred embodiments, the (e.g.hardcoat) surface layers provide any one or combination of enhancedstain and ink repellency properties, adequate smoothness, and improveddurability.

Other objects and advantages of the present invention will becomeapparent upon considering the following detailed description andappended claims, and upon reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates an article having a hard coated optical displayformed in accordance with a preferred embodiment of the presentinvention.

DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS

For the following defined terms, these definitions shall be applied,unless a different definition is given in the claims or elsewhere in thespecification.

The term “(meth)acryl” refers to functional groups including acrylates,methacrylates, acrylamides, methacrylamides, alpha-fluoroacrylates,thioacrylates and thio-methacrylates. A preferred (meth)acryl group isacrylate.

The term “monovalent perfluoropolyether moiety” refers to aperfluoropolyether chain having one end terminated by a perfluoroalkylgroup.

The term “ceramer” is a composition having inorganic oxide particles,e.g. silica, of nanometer dimensions dispersed in a binder matrix. Thephrase “ceramer composition” is meant to indicate a ceramer formulationin accordance with the present invention that has not been at leastpartially cured with radiation energy, and thus is a flowing, coatableliquid. The phrase “ceramer composite” or “coating layer” is meant toindicate a ceramer formulation in accordance with the present inventionthat has been at least partially cured with radiation energy, so that itis a substantially non-flowing solid. Additionally, the phrase“free-radically polymerizable” refers to the ability of monomers,oligomers, polymers or the like to participate in crosslinking reactionsupon exposure to a suitable source of free radicals.

The term “polymer” will be understood to include polymers, copolymers(e.g. polymers using two or more different monomers), oligomers andcombinations thereof, as well as polymers, oligomers, or copolymers thatcan be formed in a miscible blend.

Unless otherwise noted, “HFPO—” refers to the end groupF(CF(CF₃)CF₂O)_(a)CF(CF₃)— of the methyl esterF(CF(CF₃)CF₂O)_(a)CF(CF₃)C(O)OCH₃, wherein “a” averages 2 to 15. In someembodiments, a averages between 3 and 10 or a averages between 5 and 8.Such species generally exist as a distribution or mixture of oligomerswith a range of values for a, so that the average value of a may benon-integer. In one embodiment a averages 6.2. This methyl ester has anaverage molecular weight of 1,211 g/mol, and can be prepared accordingto the method reported in U.S. Pat. No. 3,250,808 (Moore et al.), thedisclosure of which is incorporated herein by reference, withpurification by fractional distillation. The recitation of numericalranges by endpoints includes all numbers subsumed within the range (e.g.the range 1 to 10 includes 1, 1.5, 3.33, and 10).

As used in this specification and the appended claims, the singularforms “a”, “an”, and “the” include plural referents unless the contentclearly indicates otherwise. Thus, for example, reference to acomposition containing “a compound” includes a mixture of two or morecompounds. As used in this specification and the appended claims, theterm “or” is generally employed in its sense including “and/or” unlessthe content clearly dictates otherwise.

Unless otherwise indicated, all numbers expressing quantities ofingredients, measurements of properties such as contact angle, and solike as used in the specification and claims understood to be modifiedin all instances by the term “about.” Accordingly, unless indicated tothe contrary, the numerical parameters set forth in the foregoingspecification and attached claims are approximations that can varydepending upon the desired properties sought to be obtained by thoseskilled in the art utilizing the teachings of the present invention. Atthe very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claims, each numericalparameter should be at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques. Notwithstanding that the numerical ranges and parameters setforth in the broad scope of the invention are approximations, thenumerical values set forth in the specific examples are reported asaccurately as possible. Any numerical value, however, inherentlycontains certain errors necessarily resulting from the standarddeviations found in their respective testing measurements.

The term “optical display”, or “display panel”, can refer to anyconventional optical displays, including but not limited tomulti-character multi-line displays such as liquid crystal displays(“LCDs”), plasma displays, front and rear projection displays, cathoderay tubes (“CRTs”), and signage, as well as single-character or binarydisplays such as light emitting diodes (“LEDs”), signal lamps, andswitches. The exposed surface of such display panels may be referred toas a “lens.” The invention is particularly useful for displays having aviewing surface that is susceptible to being touched or contacted by inkpens, markers and other marking devices, wiping cloths, paper items andthe like.

The protective coatings of the invention can be employed in a variety ofportable and non-portable information display articles. These articlesinclude PDAs, cell phones (including combination PDA/cell phones), LCDtelevisions (direct lit and edge lit), touch sensitive screens, wristwatches, car navigation systems, global positioning systems, depthfinders, calculators, electronic books, CD and DVD players, projectiontelevision screens, computer monitors, notebook computer displays,instrument gauges, instrument panel covers, signage such as graphicdisplays and the like. The viewing surfaces can have any conventionalsize and shape and can be planar or non-planar, although flat paneldisplays are preferred. The coating composition or coated film, can beemployed on a variety of other articles as well such as for examplecamera lenses, eyeglass lenses, binocular lenses, mirrors,retroreflective sheeting, automobile windows, building windows, trainwindows, boat windows, aircraft windows, vehicle headlamps andtaillights, display cases, road pavement markers (e.g. raised) andpavement marking tapes, overhead projectors, stereo cabinet doors,stereo covers, watch covers, as well as optical and magneto-opticalrecording disks, and the like.

A combination of low surface energy (e.g. anti-soiling, stain resistant,oil and/or water repellency) and durability (e.g. abrasion resistance)is desired for the coating layer for these displays while maintainingoptical clarity. The hard coating layer functions to decrease glare losswhile improving durability and optical clarity.

The surface energy can be characterized by various methods such ascontact angle and ink repellency, as determined by the test methodsdescribed in the Examples. In this application, “stain repellent” refersto a surface treatment exhibiting a static contact angle with water ofat least 70 degrees. More preferably, the contact angle is at least 80degrees and most preferably at least 90 degrees. Alternatively, or inaddition thereto, the advancing contact angle with hexadecane is atleast 50 degrees and more preferably at least 60 degrees. Low surfaceenergy results in anti-soiling and stain repellent properties as well asrendering the exposed surface easy to clean.

Another indicator of low surface energy relates to the extent to whichink from a pen or marker beads up when applied to the exposed surface.The surface layer and articles exhibit “ink repellency” when ink frompens and markers beads up into discrete droplets and can be easilyremoved by wiping the exposed surface with tissues or paper towels, suchas tissues available from the Kimberly Clark Corporation, Roswell, Ga.under the trade designation “SURPASS FACIAL TISSUE.” Durability can bedefined in terms of results from a modified oscillating sand test(Method ASTM F 735-94) carried out at 300 rpm for 15 minutes asdescribed in the Test Methods of this application. Preferably, a durablecoating exhibits an ink repellency loss value of 65 mm (75% loss) orless, more preferably 40 mm (45% loss) or less, most preferably 0 mm (noloss) of ink repellency (IR) in this test.

Coatings appropriate for use as optical hard coatings must besubstantially free of visual defects. Visual defects that may beobserved include but are not limited to pock marks, fisheyes, mottle,lumps or substantial waviness, or other visual indicators known to oneof ordinary skill in the art in the optics and coating fields. Thus, a“rough” surface as described in the Experimental has one or more ofthese characteristics, and may be indicative of a coating material inwhich one or more components of the composition are incompatible witheach other. Conversely, a substantially smooth coating, characterizedbelow as “smooth” for the purpose of the present invention, presumes tohave a coating composition in which the various components, in thereacted final state, form a coating in which the components arecompatible or have been modified to be compatible with one another andfurther has little, if any, of the characteristics of a “rough” surface.

Additionally, the surface layer preferably exhibits an initial haze ofless than 2% and/or an initial transmission of at least 90%.

Referring now to FIG. 1, a perspective view of an article (here acomputer monitor 10) is illustrated as having an optical display 12coupled within a housing 14. The optical display 12 is a substantiallytransparent material having optically enhancing properties through whicha user can view text, graphics, or other displayed information. Theoptical display 12 includes hard coating layer 18 applied to an opticalsubstrate 16. The thickness of the hardcoat layer is typically at least0.5 microns, preferably at least 1 micron, and more preferably at least2 microns. The thickness of the hardcoat layer is generally no greaterthan 25 microns. Preferably the thickness ranges from 3 microns to 5microns.

In another embodiment (not shown), the hardcoat layer described herein(i.e. comprising at least one fluorocarbon- andurethane-(meth)acryl-containing additive and at least onenon-fluorinated crosslinking agent) may be provided as a surface layerhaving an additional hard coat layer underlying the hardcoat surfacelayer. In this embodiment, the surface layer preferably has a thicknessranging from about 10 to 200 nanometers.

Various permanent and removable grade adhesive compositions may becoated on the opposite side of the substrate 16 (i.e. to that of thehardcoat 16) so the article can be easily mounted to a display surface.Suitable adhesive compositions include (e.g. hydrogenated) blockcopolymers such as those commercially available from Kraton Polymers ofWesthollow, Texas under the trade designation “Kraton G-1657”, as wellas other (e.g. similar) thermoplastic rubbers. Other exemplary adhesivesinclude acrylic-based, urethane-based, silicone-based, and epoxy-basedadhesives. Preferred adhesives are of sufficient optical quality andlight stability such that the adhesive does not yellow with time or uponweather exposure so as to degrade the viewing quality of the opticaldisplay. The adhesive can be applied using a variety of known coatingtechniques such as transfer coating, knife coating, spin coating, diecoating and the like. Exemplary adhesives are described in U.S. Pat. No.7,351,470. Several of such adhesives are commercially available from 3MCompany, St. Paul, Minn. under the trade designations 8141, 8142, and8161.

The substrate layer 16 may consist of any of a wide variety ofnon-polymeric materials, such as glass, or polymeric materials, such aspolyethylene terephthalate (PET), bisphenol A polycarbonate, cellulosetriacetate, poly(methyl methacrylate), and biaxially orientedpolypropylene which are commonly used in various optical devices. Thesubstrate may also comprise or consist of polyamides, polyimides,phenolic resins, polystyrene, styrene-acrylonitrile copolymers, epoxies,and the like. Typically the substrate will be chosen based in part onthe desired optical and mechanical properties for the intended use. Suchmechanical properties typically will include flexibility, dimensionalstability and impact resistance. The substrate thickness typically alsowill depend on the intended use. For most applications, substratethicknesses of less than about 0.5 mm are preferred, and more preferablyabout 0.02 to about 0.2 mm. Self-supporting polymeric films arepreferred. The polymeric material can be formed into a film usingconventional filmmaking techniques such as by extrusion and optionaluniaxial or biaxial orientation of the extruded film. The substrate canbe treated to improve adhesion between the substrate and the hardcoatlayer, e.g., chemical treatment, corona treatment such as air ornitrogen corona, plasma, flame, or actinic radiation. If desired, anoptional tie layer or primer can be applied to the substrate and/orhardcoat layer to increase the interlayer adhesion.

In the case of display panels, the substrate is light transmissive,meaning light can be transmitted through the substrate 16 such that thedisplay can be viewed. Both transparent (e.g. gloss) and matte lighttransmissive substrates 16 are employed in display panels 10. Mattesubstrates 16 typically have lower transmission and higher haze valuesthan typical gloss films. The matte films exhibit this propertytypically due to the presence of micron size dispersed inorganic fillerssuch as silica that diffuse light. Exemplary matte films arecommercially available from U.S.A. Kimoto Tech, Cedartown, Ga. under thetrade designation “N4D2A”. In case of transparent substrates, hardcoatcoated transparent substrates, as well as the display articles comprisedof transparent substrates, the haze value is preferably less than 5%,more preferably less than 2% and even more preferably less than 1%.Alternatively or in addition thereto, the transmission is preferablygreater than about 90%.

Various light transmissive optical films are known including but notlimited to, multilayer optical films, microstructured films such asretroreflective sheeting and brightness enhancing films, (e.g.reflective or absorbing) polarizing films, diffusive films, as well as(e.g. biaxial) retarder films and compensator films such as described inU.S. Pat. No. 7,099,083.

As described is U.S. Pat. No. 6,991,695, multilayer optical filmsprovide desirable transmission and/or reflection properties at leastpartially by an arrangement of microlayers of differing refractiveindex. The microlayers have different refractive index characteristicsso that some light is reflected at interfaces between adjacentmicrolayers. The microlayers are sufficiently thin so that lightreflected at a plurality of the interfaces undergoes constructive ordestructive interference in order to give the film body the desiredreflective or transmissive properties. For optical films designed toreflect light at ultraviolet, visible, or near-infrared wavelengths,each microlayer generally has an optical thickness (i.e., a physicalthickness multiplied by refractive index) of less than about 1 μm.However, thicker layers can also be included, such as skin layers at theouter surfaces of the film, or protective boundary layers disposedwithin the film that separate packets of microlayers. Multilayer opticalfilm bodies can also comprise one or more thick adhesive layers to bondtwo or more sheets of multilayer optical film in a laminate.

Further details of suitable multilayer optical films and relatedconstructions can be found in U.S. Pat. No. 5,882,774 (Jonza et al.),and PCT Publications WO 95/17303 (Ouderkirk et al.) and WO 99/39224(Ouderkirk et al.). Polymeric multilayer optical films and film bodiescan comprise additional layers and coatings selected for their optical,mechanical, and/or chemical properties. See U.S. Pat. No. 6,368,699(Gilbert et al.). The polymeric films and film bodies can also compriseinorganic layers, such as metal or metal oxide coatings or layers. Thecomposition of the hard coating layer 18, prior to application andcuring to the optical substrate 16, is formed from a mixture of aconventional hydrocarbon-based, and more preferably acrylate-based, hardcoat composition and a fluorocarbon- and urethane-acrylate-containingadditive. Preferred fluorocarbon- and urethane-acrylate-containingadditive compositions are described in Formulas (1), (3A), (4), (5) and(6) below. Methods for forming the hard coating compositions for each ofthe preferred embodiments are described below in the experimentalsection.

In one preferred embodiment of the present invention, the fluorocarbon-and urethane-acrylate-containing additive is a perfluoropolyetherurethane having a monovalent perfluoropolyether moiety and amulti-acrylate terminal group combined with a conventionalhydrocarbon-based (more preferably acrylate-based) hard coat material.The perfluoropolyether urethane having a monovalent perfluoropolyethermoiety and a multi-acrylate terminal group is added at between about0.01% and 10%, and more preferably between about 0.1% and 1%, of thetotal solids of the hard coat composition. The additive is of theFormula (1):R_(i)—(NHC(O)XQR_(f))_(m),—(NHC(O)OQ(A)_(p))_(n)  (1)wherein R_(i) is a residue of a multi-isocyanate; X is O, S or NR, whereR is H or lower alkyl of 1 to 4 carbon atoms; R_(f) is a monovalentperfluoropolyether moiety composed of groups comprising the formulaF(R_(fc)O)_(x)C_(d)F_(2d)—, wherein each R_(fc) independently representsa fluorinated alkylene group having from 1 to 6 carbon atoms, each xindependently represents an integer greater than or equal to 2, andwherein d is an integer from 1 to 6; Q is independently a connectinggroup of valency at least 2; A is a (meth)acryl functional group—XC(O)C(R₂)═CH₂, where R₂ is a lower alkyl of 1 to 4 carbon atoms or Hor F; m is at least 1; n is at least 1; p is 2 to 6, m+n is 2 to 10, andin which each unit referred to by the subscripts m and n is attached toan R_(i) unit.

Q can be a straight or branched chain or cycle-containing connectinggroup. Q can include a covalent bond, an alkylene, an arylene, anaralkylene, an alkarylene. Q can optionally include heteroatoms such asO, N, and S, and combinations thereof. Q can also optionally include aheteroatom-containing functional group such as carbonyl or sulfonyl, andcombinations thereof.

By their method of synthesis, these materials are necessarily mixtures.If the mole fraction of isocyanate groups is arbitrarily given a valueof 1.0, then the total mole fraction of m and n units used in makingmaterials of Formula (1) is 1.0 or greater. The mole fractions of m:nranges from 0.95:0.05 to 0.05:0.95. Preferably, the mole fractions ofm:n are from 0.50:0.50 to 0.05:0.95. More preferably, the mole fractionsof m:n are from 0.25:0.75 to 0.05:0.95 and most preferably, the molefractions of m:n are from 0.25:0.75 to 0.10:0.95. In the instances themole fractions of m:n total more than one, such as 0.15:0.90, the m unitis reacted onto the isocyanate first, and a slight excess (0.05 molefraction) of the n units are used.

In a formulation, for instance, in which 0.15 mole fractions of m and0.85 mole fraction of n units are introduced, a distribution of productsis formed in which some fraction of products formed contain no m units.There will, however, be present in this product distribution, materialsof Formula (1).

Numerous diisocyanates (di-functional isocyanates), modifieddiisocyanate materials, and higher functional isocyanates may be used asR_(i) in the present invention as the residue of multi-isocyanate andstill fall within the spirit of the present invention. Most preferably,multifunctional materials based on hexamethylene diisocyanate (“HDI”)are utilized. One commercially available derivative of HDI is Desmodur™N100, available from Bayer Polymers LLC of Pittsburgh, Pa.

Further, other diisocyanates such as toluene diisocyanate (“TDI”) orisophorone diisocyanate (“IPDI”) may also be utilized as R_(i) in thepresent invention. Non-limiting examples of aliphatic and aromaticisocyanate materials, for example, that may be used include Desmodur™3300, Desmodur™ TPLS2294, and Desmodur™ N 3600, all obtained from BayerPolymers LLC of Pittsburgh, Pa.

Materials used to make the additive of Formula (1) may be described bythe Formula: HOQ(A)_(p), which are exemplified by, for instance,1,3-glycerol dimethacrylate, available from Echo Resins Inc. ofVersailles, Mo.; and pentaerythritol triacrylate, available as SR444Cfrom Sartomer of Exton, Pa.

Typically, the additive compositions of this preferred embodiment aremade by first reacting the polyisocyanate with theperfluoropolyether-containing alcohol, thiol, or amine, followed byreaction with the hydroxyl functional multiacrylate, usually in anon-hydroxylic solvent and in the presence of a catalyst such as anorganotin compound. Alternatively, the additives of this preferredembodiment are made by reacting the polyisocyanate with the hydroxylfunctional multiacrylate, followed by reaction with theperfluoropolyether-containing alcohol, thiol, or amine, usually in anon-hydroxylic solvent and in the presence of a catalyst such as anorganotin compound. In addition, the additives could be made by reactingall three components simultaneously, usually in a non-hydroxylic solventand in the presence of a catalyst such as an organotin compound.

One representative structure (2) of perfluoropolyether urethanes withmulti-acrylate terminal groups of Formula (1) is shown below as:

which is the reaction product of the biuret of HDI with one equivalentof HFPO oligomer amidol (F(CF(CF₃)CF₂O)_(a)CF(CF₃)C(O)NHCH₂CH₂OH) andfurther with two equivalents of pentaerythritol triacrylate, wherein “a”averages 2 to 15. In some embodiments, a averages between 3 and 10 or aaverages between 5 and 8.

In another embodiment, the additive composition is of the Formula (3A):R_(f)-Q-(XC(O)NHQOC(O)C(R)═CH₂)_(f)  (3A)where R_(f), Q and X are the same as previously described with referenceto Formula (1) and f is 1-5.

One preferred perfluoropolyether-substituted urethane(meth)acrylate thatmeets the description of Formula (3A) is described more specifically inFormula (3B):HFPO-Q-(XC(O)NHQOC(O)C(R)═CH₂)_(f)  (3B)

Two preferred HFPO-substituted urethane acrylates that can be utilizedinclude HFPO—C(O)NHC₂H₄OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂ andHFPO—C(O)NHC(C₂H₅)(CH₂OC(O)NHC₂H₄OC(O)C(CH₃)═CH₂)₂.

In another embodiment, the additive composition is of the Formula (4):R_(i)—(NHC(O)XQR_(f))_(m),—(NHC(O)OQ(A)_(p))_(n),—(NHC(O)XQG)_(o),—(NCO)_(q)  (4)wherein R_(i) is a residue of a multi-isocyanate; X, R_(f) and Q are thesame as previously described with reference to Formula (1). A is a(meth)acryl functional group —XC(O)C(R₂)═CH₂, where R₂ is a lower alkylof 1 to 4 carbon atoms or H or F; G is selected from the groupconsisting of an alkyl, an aryl, an alkaryl and an aralkyl. G optionallycontains heteroatoms such as O, N, and S, and combinations thereof. Galso optionally has heteroatom-containing functional groups such ascarbonyl, sulfonyl, and combinations thereof. Further, G may have acombination of heteroatoms and heteroatom-containing functional groups.G optionally contains pendant or terminal reactive groups. The reactivegroup may include (meth)acryl groups, vinyl groups, allyl groups and—Si(OR₃)₃ groups, where R₃ is a lower alkyl of 1 to 4 carbon atoms. Galso optionally has fluoroalkyl or perfluoroalkyl groups. In Formula(4), m is at least 1; n is at least 1; o is at least 1; p is 2 to 6; andq is 0 or greater.

(m+n+o+q)═N_(NCO), the number of isocyanate groups originally appendedto R_(i); and the quantity (m+n+o)/N_(NCO) is greater than or equal to0.67, and in which each unit referred to by the subscripts m, n, o, andq is attached to an R_(i) unit. Preferably R_(fc) is —CF(CF₃)CF₂—.

The monoalcohol, monothiol or monoamine HXQG used in making materials ofFormula (4) may include materials such as C₄F₉SO₂N(CH₃)CH₂CH₂OH,H₂NCH₂CH₂CH₂(SiOCH₃)₃, HSCH₂CH₂CH₂Si(OCH₃)₃, and HEA(hydroxyethylacrylate).

In another embodiment, the additive composition is of the Formula (5):(R_(i))_(c)—(NHC(O)XQR_(f))_(m),—(NHC(O)OQ(A)_(p))_(n),—(NHC(O)XQG)_(o),(R_(f)(Q)(XC(O)NH)_(y))_(z)—,—(NHC(O)XQD(QXC(O)NH)_(u))_(s)—,D₁(QXC(O)NH)_(y))_(zz)—,—(NHC(O)OQ(A)_(t)Q₁Q(A)_(t)OC(O)NH))_(v)—,—(NCO)_(w)  (5)wherein R_(i) is the residue of a multi-isocyanate; c is 1 to 50; X,R_(f), and Q are the same as previously described with reference toFormula (1). A and G are the same as previously described with referenceto Formula 4. D is alkylene, arylene, alkarylene, fluoroalkylene,perfluoroalkylene or aralkylene; and optionally contains heteroatomssuch as O, N, and S. D₁ is alkyl, aryl, alkaryl, fluoroalkyl,perfluoroalkyl or aralkyl; optionally containing heteroatoms such as O,N, and S. Q₁ is a connecting group defined in the same way as Q. InFormula 5, m or z is at least 1; n or v is at least 1; y isindependently 2 or greater; o, s, v, w, z and zz are 0 or greater. Thesum of s, v, z and zz is at least one. Therefore, at least one of thesegroups is present.

(m+n+o+[(u+l)s]+2v+w+yz+y(zz))=cN_(NCO) the number of isocyanate groupsoriginally appended to R_(i). The quantity(m+n+o+([(u+l)s]+2v+yz+y(zz))/(cN_(NCO)) is greater than or equal toleast 0.75. In Formula 5, p is 2 to 6; t is 1 to 6; and u isindependently 1 to 3; in which each unit referred to by the subscriptsm, n, o, s, v, w, z and zz is attached to an R_(i) unit. PreferablyR_(fc) is —CF(CF₃)CF₂—.

In this embodiment, when added to the conventional hydrocarbon-basedhard coating material, care must be taken in choosing the ratios andamounts of reactive components to avoid highly crosslinked urethanepolymer gels. For instance, if a trifunctional isocyanate is to be usedwith a multifunctional alcohol, the amount of multifunctional alcoholshould be limited to avoid forming a crosslinked network. For highernumbers of c for (R_(i))_(c) groups, it is preferred that theformulation be based primarily on diols and diisocyanates.

The materials used to make the additive of Formula (5) include those ofthe formula R_(f)(Q)(XH)_(y), which is exemplified byHFPO—C(O)NHCH₂CH₂CH₂N(CH₂CH₂OH)₂.

The materials used to make the additive of Formula (5) include those ofthe formula: HXQDQXH, which is exemplified by hydrocarbon polyols suchas HO(CH₂)₁₀OH and fluorochemical diols such as HOCH₂(CF₂)₄CH₂OH.

The materials used to make the additive of Formula (5) may include thoseof the formula D(QXH)_(y))_(zz), which is exemplified by fluorochemicaldiols C₄F₉SO₂N(CH₂CH₂OH)₂.

The materials used to make the additive of Formula (5) may also includethose of the formula HOQ(A)_(t)Q₁Q(A)_(t)OH, which is exemplified byhydantoin hexaacrylate (HHA), prepared as described in Example 1 of U.S.Pat. No. 4,262,072 to Wendling et al, andCH₂═C(CH₃)C(O)OCH₂CH(OH)CH₂O(CH₂)₄OCH₂CH(OH)CH₂OC(O)C(CH₃)═CH₂.

In still another embodiment the additive composition is of the Formula(6):(R_(i))_(c)—(NHC(O)XQR_(f))_(m),—(NHC(O)OQ(A)_(p))_(n),—(NHC(O)XQG)_(o),—(NHC(O)XQR_(f2)(QXC(O)NH)_(u))_(r)—,—(NHC(O)XQD(QXC(O)NH)_(u))_(s)—,D₁(QXC(O)NH)_(y))_(zz),—(NHC(O)OQ(A)_(t)Q₁Q(A)_(t)OC(O)NH))_(v)—,—(NCO)_(w)  (6)wherein R_(i) is the residue of a multi-isocyanate; c is 1 to 50; X,R_(f), Q, Q₁, A, G, D, and D₁ are the same as previously described withreference to Formula (5). R_(f2) is a multi-valent fluoropolyethermoiety, R_(f2) is composed of groups comprising the formulaY((R_(fc1)O)_(x)C_(d1)F_(2d1))_(b), wherein each R_(fc1) independentlyrepresents a fluorinated alkylene group having from 1 to 6 carbon atoms:each x independently represents an integer greater than or equal to 2,and d1 is an integer from 0 to 6. Y represents a polyvalent organicgroup or covalent bond having a valence of b, and b represents aninteger greater than or equal to 2. In Formula (5), r is at least 1; nor v is at least 1; y is independently 2 or greater. Further, m, o, s,v, w and zz are 0 or greater.

(m+n+o+[(u+l)r]+[(u+l)s]+2v+w+y(zz))=cN_(NCO) the number of isocyanategroups originally appended to R_(i). The quantity(m+n+o+[(u+l)r]+[(u+l)s]+2v+y(zz))/(cN_(NCO)) is greater than or equalto least 0.75.

In Formula (5), p is 2 to 6; t is 1 to 6; u is independently 1 to 3; inwhich each unit referred to by the subscripts m, n, o, r, s, v, w, andzz is attached to an R_(i) unit. R_(fc1) is preferably independentlyselected from —CF(CF₃)CF₂—, —CF₂CF₂CF₂—, and(—CH₂C(R)(CH₂OCH₂C_(d)F_(2d+1))CH₂—)_(aa) where aa is 2 or greater and dand R are defined above.

The materials used to make the additive of Formula (9) may also includethose of the formula HXQR_(f2)QXH, which is exemplified by(H(OCH₂C(CH₃)(CH₂OCH₂CF₃)CH₂)_(aa)OH) (Fox-Diol, having a MW about 1342and available from Omnova Solutions Inc. of Akron, Ohio).

For each of the formulas (i.e. Formulas 1-6) described herein, when X isO, Q is typically not methylene and thus contains two or more carbonatoms. In some embodiments, X is S or NR. In some embodiments, Q is analkylene having at least two carbon atoms. In other embodiments, Q is astraight chain, branched chain, or cycle-containing connecting groupselected from arylene, aralkylene, and alkarylene. In yet otherembodiments, Q is a straight chain, branched chain, or cycle-containingconnecting group containing a heteroatom such as O, N, and S and/or aheteroatom containing functional groups such as carbonyl and sulfonyl.In other embodiments, Q is a branched or cycle-containing alkylene groupthat optionally contains heteroatoms selected from O, N, S and/or aheteroatom-containing functional group such as carbonyl and sulfonyl. Insome embodiments Q contains a nitrogen containing group such as amide.

The fluorocarbon- and urethane-(meth)acryl additive(s) described hereincan be employed as the sole perfluoropolyether containing additive in ahardcoat composition. Alternatively, however, the additive(s) describedherein may be employed in combination with various other fluorinatedcompounds having at least one moiety selected from fluoropolyether,fluoroalkyl, and fluoroalkylene linked to at least one free-radicallyreactive group with a non-urethane linking group. In these embodiments,the fluorocarbon- and urethane-(meth)acryl compositions(s) can be addedto the curable mixture such that the weight ratio of the fluorocarbonurethane additive to non-urethane fluorinated material(s) is 1:1,preferably 2:1 and most preferably 3:1. Within these preferred ratios itis possible to have the total weight percent fluorine (F) of the curablemixture comprise from 0.5-25 wt % F, preferably 0.5 to 10 wt % F andmost preferably 0.5 to 5 wt % F.

The perfluoropolyether moiety of the urethane is preferably a HFPOmoiety, as previously described. Further, the fluorinated moiety of thesecond (non-urethane) compound is also preferably a HFPO moiety.

In some embodiments, the non-urethane linking group is a divalent groupselected from an alkylene, arylene, or combinations thereof andoptionally containing a divalent group selected from carbonyl, ester,amide, thioester or sulfonamido, and combinations thereof. In otherembodiments, the linking group is a sulfur-containing heteroalkylenegroup containing a divalent group selected from carbonyl, ester, amide,thioester or sulfonamido, and combinations thereof. In otherembodiments, the linking group is an oxygen-containing heteroalkylenegroup containing a divalent group selected from carbonyl, ester,thioester, sulfonamido, and combinations thereof. In yet otherembodiments, the linking group is a nitrogen-containing heteroalkylenegroup containing a divalent group selected from carbonyl, amide,thioester, or sulfonamido, and combinations thereof.

A variety of (per)fluoropolyether(meth)acryl compounds may be employedin the (e.g. hardcoat) coating compositions in combination with thefluorocarbon- and urethane-(meth)acryl compositions.Perfluoropolyether(meth)acryl compounds can be represented by thefollowing Formula (7):(R_(f))—[(W)—(R_(A))]_(W)  (Formula 7)wherein R_(f) is a (per)fluoropolyether group; W is a linking group; andR_(A) is a is a free-radically reactive such as (meth)acryl, —SH, allyl,or vinyl, and is preferably a (meth)acryl group or —COCF═CH₂; and w is 1or 2.

The perfluoropolyether group R_(f) can be linear, branched, cyclic, orcombinations thereof and can be saturated or unsaturated. Theperfluoropolyether has at least two catenated oxygen heteroatoms.Exemplary perfluoropolyethers include, but are not limited to, thosethat have perfluorinated repeating units selected from the group of—(C_(p)F_(2p))—, —(C_(p)F_(2p)O)—, —(CF(Z))—, —(CF(Z)O)—,—(CF(Z)C_(p)F_(2p)O)—, —(C_(p)F_(2p)CF(Z)O)—, —(CF₂CF(Z)O)—, orcombinations thereof. In these repeating units, p is typically aninteger of 1 to 10. In some embodiments, p is an integer of 1 to 8, 1 to6, 1 to 4, or 1 to 3. The group Z is a perfluoroalkyl group,perfluoroether group, perfluoropolyether, or a perfluoroalkoxy group,all of which can be linear, branched, or cyclic. The Z group typicallyhas no more than 12 carbon atoms, no more than 10 carbon atoms, or nomore than 9 carbon atoms, no more than 4 carbon atoms, no more than 3carbon atoms, no more than 2 carbon atoms, or no more than 1 carbonatom. In some embodiments, the Z group can have no more than 4, no morethan 3, no more than 2, no more than 1, or no oxygen atoms. In theseperfluoropolyether structures, the different repeat units can bedistributed randomly along the chain.

R_(f) can be monovalent or divalent. In some compounds where R_(f) ismonovalent, the terminal groups can be (C_(p)F_(2p+1))—,(C_(p)F_(2p+1)O)—, (X′C_(p)F_(2p)O)—, or (X′C_(p)F_(2p+1))— where X ishydrogen, chlorine, or bromine and p is an integer of 1 to 10. In someembodiments of monovalent R_(f) groups, the terminal group isperfluorinated and p is an integer of 1 to 10, 1 to 8, 1 to 6, 1 to 4,or 1 to 3. Exemplary monovalent R_(f) groups includeCF₃O(C₂F₄O)_(n)CF₂—, C₃F₇O(CF₂CF₂CF₂O)_(n)CF₂CF₂—, andC₃F₇O(CF(CF₃)CF₂O)_(n)CF(CF₃)— wherein n has an average value of 0 to50, 1 to 50, 3 to 30, 3 to 15, or 3 to 10.

Suitable structures for divalent R_(f) groups include, but are notlimited to, —CF₂O(CF₂O)_(q)(C₂F₄O)—CF₂—, —(CF₂)₃O(C₄F₈O)_(n)(CF₂)₃—,—CF₂O(C₂F₄O)_(n)CF₂—, —CF₂CF₂O(CF₂CF₂CF₂O)_(n)CF₂CF₂—, and—CF(CF₃)(OCF₂CF(CF₃))_(s)OC_(t)F_(2t)O(CF(CF₃)CF₂O)_(n)CF(CF₃)—, whereinq has an average value of 0 to 50, 1 to 50, 3 to 30, 3 to 15, or 3 to10; n has an average value of 0 to 50, 3 to 30, 3 to 15, or 3 to 10; shas an average value of 0 to 50, 1 to 50, 3 to 30, 3 to 15, or 3 to 10;the sum (n+s) has an average value of 0 to 50 or 4 to 40; the sum (q+n)is greater than 0; and t is an integer of 2 to 6.

As synthesized, compounds according to Formula (7) typically include amixture of R_(f) groups. The average structure is the structure averagedover the mixture components. The values of q, n, and s in these averagestructures can vary, as long as the compound has a number averagemolecular weight of at least about 400. Compounds of Formula (7) oftenhave a molecular weight (number average) of 400 to 5000, 800 to 4000, or1000 to 3000.

The linking group W between the perfluoropolyether segment and(meth)acryl or —COCF═CH₂ endgroup includes a divalent group selectedfrom an alkylene, arylene, heteroalkylene, or combinations thereof andan optional divalent group selected from carbonyl, ester, amide,sulfonamido, or combinations thereof. W can be unsubstituted orsubstituted with an alkyl, aryl, halo, or combinations thereof. The Wgroup typically has no more than 30 carbon atoms. In some compounds, theW group has no more than 20 carbon atoms, no more than 10 carbon atoms,no more than 6 carbon atoms, or no more than 4 carbon atoms. Forexample, W can be an alkylene, an alkylene substituted with an arylgroup, or an alkylene in combination with an arylene or an alkyl etheror alkyl thioether linking group.

The perfluoropolyether acrylate compounds (e.g. of Formula 7) can besynthesized by known techniques such as described in U.S. Pat. Nos.3,553,179 and 3,544,537 as well as U.S. Pat. No. 7,094,829,“Fluorochemical Composition Comprising a Fluorinated polymer andTreatment of a Fibrous Substrate Therewith”.

Suitable (non-urethane) perfluoropolyether fluorocarbon(meth)acrylcompounds include for example HFPO—C(O)NHCH₂CH₂OC(O)CH═CH₂,HFPO—C(O)NHCH₂CH₂OCH₂CH₂OCH₂CH₂OC(O)CH═CH₂HFPO—C(O)NH—(CH₂)₆OC(O)CH═CH₂and various other (per)fluoropolyether acryl compounds such as describedin U.S. Pat. No. 7,342,080 and US Publication No. 2005/0249940;incorporated by reference.

The (non-urethane) fluoropolyether poly(meth)acryl compound may alsohave the formula (HFPO—)_(n)Q₃(X)_(m) wherein n is 1 to 3;

Q₃ is a straight chain, branched chain or cycle-containing connectinggroup having a valency of at least 2 and is selected from the groupconsisting of a covalent bond, an alkylene, an arylene, an aralkylene,an alkarylene; optionally containing heteroatoms O, N, and S, aheteroatom-containing functional group such as carbonyl or sulfonyl, andcombinations thereof; and X is a free-radically reactive group such as(meth)acryl, —SH, allyl, or vinyl, and is preferably a (meth)acrylfunctional group -AC(O)C(R)═CH₂, where A is O, S or NR₁, R is a loweralkyl of 1 to 4 carbon atoms or H or F, R₁ is H or lower alkyl of 1 to 4carbon atoms, and m is 2-10.

One compound is B—O(CH₂CH(OB)CH₂O)nCH₂CH(OB)CH₂O—B wherein n ranges from0 to 20, B is independently H, —C(O)CH═CH₂, or —C(O)—HFPO, and in whichat least one B is —C(O)—HFPO and at least two B are —C(O)CH═CH₂.

The (non-urethane) fluoropolyether poly(meth)acryl compound may be thereaction product of A)

whereinR₂ is hydrogen, alkyl, aryl, arylalkyl, alkylaryl, fluoroalkyl, acryl,HFPO—C(O)—,R₃ is independently H or CH₂═C(CH₃)C(O)—OC₂H₄NHC(O)—,R₄ is alkyl, aryl, arylalkyl, alkylaryl, fluoroalkyl, acryl, HFPO—C(O)—,or CH₂═C(CH₃)C(O)—OC₂H₄NHC(O)—,R₅ is alkyl, aryl, arylalkyl, alkylaryl, fluoroalkyl, acryl, HFPO—C(O)—,or CH₂═C(CH₃)C(O)—OCH₂CH(OH)CH₂—,R₆ is independently H or CH₂═C(CH₃)C(O)—OCH₂CH(OH)CH₂—,and n ranges from an average about 2 to 3.

The (e.g. non-urethane) fluoropolyether poly(meth)acryl compound mayinclude any one or combination of the following compounds

HFPO—C(O)NHC(CH₂OC(O)CH═CH₂)₃;

HFPO—C(O)N(CH₂CH₂OC(O)CH═CH₂)₂;

HFPO—C(O)NHCH₂CH₂N(C(O)CH═CH₂)CH₂OC(O)CH═CH₂;

HFPO—C(O)NHC(CH₂OC(O)CH═CH₂)₂H;

HFPO—C(O)NHC(CH₂OC(O)CH═CH₂)₂CH₃;

HFPO—C(O)NHC(CH₂OC(O)CH═CH₂)₂CH₂CH₃;

HFPO—C(O)NHCH₂CH(OC(O)CH═CH₂)CH₂OC(O)CH═CH₂;

HFPO—C(O)NHCH₂CH₂CH₂N(CH₂CH₂OC(O)CH═CH₂)₂;

HFPO—C(O)OCH₂C(CH₂OC(O)CH═CH₂)₃;

HFPO—C(O)NH(CH₂CH₂N(C(O)CH═CH₂))₄CH₂CH₂NC(O)—HFPO;

CH₂═CHC(O)OCH₂CH(OC(O)HFPO)CH₂OCH₂CH(OH)CH₂OCH₂CH(OC(O)HFPO)CH₂OCOCH═CH₂;and

HFPO—CH₂O—CH₂CH(OC(O)CH═CH₂)CH₂OC(O)CH═CH₂

In other embodiments, the non-urethane fluoropolyether poly(meth)acrylcompound may be a compound preparable by Michael-type addition of areactive (per)fluoropolyether with a poly(meth)acrylate, such as theadduct of HFPO—C(O)N(H)CH₂CH₂CH₂N(H)CH₃ with trimethylolpropanetriacrylate (TMPTA). Such (per)fluoropolyether acrylate compounds arefurther described in U.S. Pat. No. 7,342,080.

Other non-urethane fluoropolyether poly(meth)acryl compounds includethose disclosed in U.S. Pat. Nos. 3,810,874 and 4,321,404. Arepresentative compound is given by the structureCH₂═CHC(O)OCH₂CF₂O(CF₂CF₂O)_(mm)(CF₂O)_(nn)CH₂OC(O)CH═CH₂,

where mm and nn designate that the number of randomly distributedperfluoroethyleneoxy and perfluoromethyleneoxy backbone repeating units,respectively, mm and nn having independently values, for example from 1to 50, and the ratio of mm/nn is 0.2 to 1 to 5/1.

Still other non-urethane fluoropolyether compounds include thiols suchas HFPO—C(O)NHCH₂CH₂OC(O)CH₂SH and vinyl compounds such asHFPO—C(O)NHCH₂CH═CH₂, and HFPO—C(O)NHCH₂CH₂OCH═CH₂.

In one synergistic combination, a perfluoropolyether urethane having aperfluoropolyether moiety and a multi-(meth)acryl terminal group isemployed in combination with a (non-urethane) monofunctionalperfluoropolyether compound having a perfluoropolyether moiety linked toa (meth)acryl group. Typically, the perfluoropolyether moiety is aterminal group of the compound. Likewise, the (meth)acryl group is alsotypically a terminal group. In another embodiment, the second(non-urethane) perfluoropolyether compound typically has a higher weightpercent fluorine than the perfluoropolyether urethane multi-(meth)acrylcompound. It is surmised that the monofunctional perfluoropolyethercompound is the major contributor to the high contact angles; whereasthe perfluoropolyether urethane multi-(meth)acryl compoundcompatibilizes the monofunctional perfluoropolyether compound. Thisinteraction allows higher concentration of monofunctionalperfluoropolyether compound to be incorporated without phase separation.In yet another embodiment, a perfluoropolyether urethane having aperfluoropolyether moiety and a multi-(meth)acryl terminal group isemployed in combination with a (non-urethane) multi-functionalperfluoropolyether compound having a perfluoropolyether moiety linked toat least two (meth)acryl group. Alternatively, a perfluoropolyetherurethane monoacrylate can be employed in combination with a(non-urethane) mono- or multi-(meth)acryl perfluoropolyether compound.

The fluorocarbon- and urethane(meth)acryl additives (e.g. such as thoseof Formulas (1), (3A), (4), (5) or (6)), optionally in combination withvarious other (per)fluoropolyether(meth)acryl compounds, may also becombined with one or more other (non-urethane) fluorinated compounds toimprove the compatibility of the mixture.

A class of free-radically reactive fluoroalkyl or fluoroalkylenegroup-containing compatibilizers includes compounds of the respectivechemical formulas: R_(ff)Q₃(X₁)_(n1) and (X₁)_(n1)Q₃R_(ff2)Q₃(X₁)_(n1)),where R_(ff) is a fluoroalkyl, R_(ff2) is a fluoroalkylene, Q₃ is aconnecting group of valency at least 2 and is selected from the groupconsisting of a covalent bond, an alkylene, an arylene, an aralkylene,an alkarylene group, a straight or branched chain or cycle-containingconnecting group optionally containing heteroatoms such as O, N, and Sand optionally a heteroatom-containing functional group such as carbonylor sulfonyl, and combinations thereof; X₁ is a free-radically reactivegroup selected from (meth)acryl, —SH, allyl, or vinyl groups and n1 isindependently 1 to 3. Typical Q₃ groups include: —SO₂N(R)CH₂CH₂—;—SO₂N(CH₂CH₂)₂—; —(CH₂)_(m)—; —CH₂O(CH₂)₃—; and —C(O)NRCH₂CH₂—, where Ris H or lower alkyl of 1 to 4 carbon atoms and m is 1 to 6. Preferablythe fluoroalkyl or fluoroalkylene group is a perfluoroalkyl orperfluoroalkylene group. One preferred class of fluoroalkyl- oralkylene-substituted compatibilizers meeting these criteria for use inthe composition of the hard coat layer 18 is theperfluorobutyl-substituted acrylate compatibilizers. Exemplary,non-limiting perfluorobutyl-substituted acrylate compatibilizers meetingthese criteria and useful in the present invention include one or moreof C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH═CH₂, C₄F₉SO₂N(CH₂CH₂OC(O)CH═CH₂)₂, orC₄F₉SO₂N(CH₃)CH₂CH₂OC(O)C(CH₃)═CH₂. The free-radically reactivefluoroalkyl or fluoroalkylene group-containing compatibilizers describedabove are preferably added at between about 0.5% and 20%, and morepreferably between about 1% and 10%, of the total solids of the hardcoat composition.

One non-limiting example of a preferred fluoroalkyl-substitutedcompatibilizer that may be utilized in the composition of the hard coatlayer 18 is: (1H,1H,2H,2H)-perfluorodecyl acrylate, available fromLancaster Synthesis of Windham, N.H. Numerous other (meth)acrylcompounds with perfluoroalkyl moieties that may also be utilized in thecomposition of the hard coat layer are mentioned in U.S. Pat. No.4,968,116, to Hulme-Lowe et al., and in U.S. Pat. No. 5,239,026(including perfluorocyclohexylmethyl methacrylate), to Babirad et al.,which are herein incorporated by reference. Other fluorochemical(meth)acrylates that meet these criteria and may be utilized include,for example, 2,2,3,3,4,4,5,5-octafluorohexanediol diacrylate and ω-hydro2,2,3,3,4,4,5,5-octafluoropentyl acrylate (H—C₄F₈—CH₂O—C(O)—CH═CH₂).Other fluorochemical (meth)acrylates that may be used alone, or asmixtures, are described in U.S. Pat. No. 6,238,798, to Kang et al., andherein incorporated by reference.

Another compatibilizer that may be used is a fluoroalkyl- orfluoroalkylene-substituted thiol or polythiol. Non-limiting examples ofthis type of compatibilizer includes one or more of the following:C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH₂SH, C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH₂CH₂SH,C₄F₉SO₂N(CH₃)CH₂CH₂SH, and C₄F₉SO₂N(CH₃)CH(OC(O)CH₂SH)CH₂OC(O)CH₂SH.

In some embodiments, as little as 1 wt-% of the non-urethane fluorinatedcompound will phase separate from a hydrocarbon multifunctional acrylatesuch as trimethyol propane triacrylate. Such phase separation isundesirable in the hardcoats of this invention since it can lead tooptically nonuniform coatings. In these embodiments, the fluorocarbon-and urethane-(meth)acryl compositions(s) can be added to the curablemixture such that the weight ratio of the fluorocarbon urethane additiveto non-urethane perfluoropolyether, fluoroalkyl, orfluoroalkylene(meth)acryl compound is 1:1, preferably 2:1 and mostpreferably 3:1. Within these preferred ratios the total weight percentfluorine of the curable mixture may comprise from 0.5-25 wt-% fluorine,preferably 0.5 to 10 wt-% fluorine, and most preferably 0.5 to 5-wt %fluorine, without the non-urethane fluorinated (meth)acryl compoundphase separating from the mixture. The non-urethane containingperfluoropolyether can have molecular weights of greater than 300 g/molto 3000 g/mol, contain mono(meth)acryl functionality, ormulti-(meth)acryl functionality. The (meth)acryl functionality can belocated at one or both termini or as a branch point in the molecule.

The hardcoat may be provided as a single layer disposed on an opticalsubstrate. In this construction, the total of all (per)fluorinatedcompounds, (e.g. the perfluoropolyether urethane(s) alone or incombination with other fluorinated compounds) ranges from 0.01% to 10%,and more preferably from 0.1% to 1%, of the total solids of the hardcoat composition. For embodiments wherein a (e.g. inorganicparticle-containing) hardcoat layer is disposed between the opticalsubstrate and hardcoat surface layer, the amount of perfluoropolyetherurethane(s) in the coating compositions ranges from 0.01 to 50 wt-%solids, and more preferably from 1 to 25 wt-% solids; whereas thevarious other (per)fluoropolyether acryl compounds may be present atweight percents from 1 to 20%, and preferably from 1 to 10%. Preferably,the ratio of fluorocarbon- and urethane-(meth)acryl-containing additiveto other non-urethane fluorinated compounds is at least 1 to 1 and morepreferably is about 3 to 1.

The conventional hard coat material used as a portion of layer 18 in anyof the preferred embodiments described above is a hydrocarbon-basedmaterial well known to those of ordinary skill in the optical arts. Mostpreferably, the hydrocarbon-based material is an acrylate-based hardcoat material. One preferable hard coat material for use in the presentinvention is based on PETA (pentaerythritol tri/tetra acrylate). Onecommercially available form of pentaerythritol triacrylate (“PET3A”) isSR444C and one commercially available form of pentaerythritoltetraacrylate (“PET4A”) is SR295, each available from Sartomer Companyof Exton, Pa.

However, other crosslinking agents may be used in the present invention.Useful crosslinking agents include, for example, poly(meth)acrylmonomers selected from the group consisting of (a) di(meth)acrylcontaining compounds such as 1,3-butylene glycol diacrylate,1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediolmonoacrylate monomethacrylate, ethylene glycol diacrylate, alkoxylatedaliphatic diacrylate, alkoxylated cyclohexane dimethanol diacrylate,alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycoldiacrylate, caprolactone modified neopentylglycol hydroxypivalatediacrylate, caprolactone modified neopentylglycol hydroxypivalatediacrylate, cyclohexanedimethanol diacrylate, diethylene glycoldiacrylate, dipropylene glycol diacrylate, ethoxylated (10) bisphenol Adiacrylate, ethoxylated (3) bisphenol A diacrylate, ethoxylated (30)bisphenol A diacrylate, ethoxylated (4) bisphenol A diacrylate,hydroxypivaldehyde modified trimethylolpropane diacrylate, neopentylglycol diacrylate, polyethylene glycol (200) diacrylate, polyethyleneglycol (400) diacrylate, polyethylene glycol (600) diacrylate,propoxylated neopentyl glycol diacrylate, tetraethylene glycoldiacrylate, tricyclodecanedimethanol diacrylate, triethylene glycoldiacrylate, tripropylene glycol diacrylate; (b) tri(meth)acrylcontaining compounds such as glycerol triacrylate, trimethylolpropanetriacrylate, ethoxylated triacrylates (e.g., ethoxylated (3)trimethylolpropane triacrylate, ethoxylated (6) trimethylolpropanetriacrylate, ethoxylated (9) trimethylolpropane triacrylate, ethoxylated(20) trimethylolpropane triacrylate), propoxylated triacrylates (e.g.,propoxylated (3) glyceryl triacrylate, propoxylated (5.5) glyceryltriacrylate, propoxylated (3) trimethylolpropane triacrylate,propoxylated (6) trimethylolpropane triacrylate), trimethylolpropanetriacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate; (c) higherfunctionality (meth)acryl containing compounds such asditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate,ethoxylated (4) pentaerythritol tetraacrylate, caprolactone modifieddipentaerythritol hexaacrylate; (d) oligomeric(meth)acryl compounds suchas, for example, urethane acrylates, polyester acrylates, epoxyacrylates; polyacrylamide analogues of the foregoing; and combinationsthereof. Such compounds are widely available from vendors such as, forexample, Sartomer Company of Exton, Pa.; UCB Chemicals Corporation ofSmyrna, Ga.; and Aldrich Chemical Company of Milwaukee, Wis. Additionaluseful (meth)acrylate materials include hydantoin moiety-containingpoly(meth)acrylates, for example, as described in U.S. Pat. No.4,262,072 (Wendling et al.).

It is typically preferred to maximize the concentration of crosslinkerparticularly since non-fluorinated (meth)acrylate crosslinkers aregenerally less expensive than fluorinated compounds. Accordingly, thecoating compositions described herein typically comprise at least 20wt-% crosslinking agent(s). The total amount of crosslinking agent(s)may comprise at least 50 wt-% and may be for example at least 60 wt-%,at least 70 wt-%, at least 80 wt-%, at least 90 wt-% and even about 95wt-% of the coating composition.

To facilitate curing, polymerizable compositions according to thepresent invention may further comprise at least one free-radical thermalinitiator and/or photoinitiator. Typically, if such an initiator and/orphotoinitiator are present, it comprises less than about 10 percent byweight, more typically less than about 5 percent of the polymerizablecomposition, based on the total weight of the polymerizable composition.Free-radical curing techniques are well known in the art and include,for example, thermal curing methods as well as radiation curing methodssuch as electron beam or ultraviolet radiation. Further detailsconcerning free radical thermal and photopolymerization techniques maybe found in, for example, U.S. Pat. No. 4,654,233 (Grant et al.); U.S.Pat. No. 4,855,184 (Klun et al.); and U.S. Pat. No. 6,224,949 (Wright etal.).

Useful free-radical thermal initiators include, for example, azo,peroxide, persulfate, and redox initiators, and combinations thereof.

Useful free-radical photoinitiators include, for example, those known asuseful in the UV cure of acrylate polymers. Such initiators includebenzophenone and its derivatives; benzoin, alpha-methylbenzoin,alpha-phenylbenzoin, alpha-allylbenzoin, alpha-benzylbenzoin; benzoinethers such as benzil dimethyl ketal (commercially available under thetrade designation “IRGACURE 651” from Ciba Specialty ChemicalsCorporation of Tarrytown, N.Y.), benzoin methyl ether, benzoin ethylether, benzoin n-butyl ether; acetophenone and its derivatives such as2-hydroxy-2-methyl-1-phenyl-1-propanone (commercially available underthe trade designation “DAROCUR 1173” from Ciba Specialty ChemicalsCorporation) and 1-hydroxycyclohexyl phenyl ketone (commerciallyavailable under the trade designation “IRGACURE 184”, also from CibaSpecialty Chemicals Corporation);2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanonecommercially available under the trade designation “IRGACURE 907”, alsofrom Ciba Specialty Chemicals Corporation);2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanonecommercially available under the trade designation “IRGACURE 369” fromCiba Specialty Chemicals Corporation); aromatic ketones such asbenzophenone and its derivatives and anthraquinone and its derivatives;onium salts such as diazonium salts, iodonium salts, sulfonium salts;titanium complexes such as, for example, that which is commerciallyavailable under the trade designation “CGI 784 DC”, also from CibaSpecialty Chemicals Corporation); halomethylnitrobenzenes; and mono- andbis-acylphosphines such as those available from Ciba Specialty ChemicalsCorporation under the trade designations “IRGACURE 1700”, “IRGACURE1800”, “IRGACURE 1850”, “IRGACURE 819” “IRGACURE 2005”, “IRGACURE 2010”,“IRGACURE 2020” and “DAROCUR 4265”. Combinations of two or morephotoinitiators may be used. Further, sensitizers such as 2-isopropylthioxanthone, commercially available from First Chemical Corporation,Pascagoula, Miss., may be used in conjunction with photoinitiator(s)such as “IRGACURE 369”.

The composition of any of these embodiments is applied to an opticalsubstrate layer or light transmissible substrate and photocured to formthe easy to clean, stain and ink repellent light transmissible surfacelayer. The presence of the urethane functionality, in addition to thefluorocarbon component, in the additive can eliminate the need forcomonomers introduced to the composition to compatibilize thefluorochemical component with the hydrocarbon-based crosslinker.

The polymerizable coating composition for use as the surface layer orunderlying hardcoat layer preferably contains surface modified inorganicparticles that add mechanical strength to the resultant coating.

A variety of inorganic oxide particles can be used in the hardcoat. Theparticles are typically substantially spherical in shape and relativelyuniform in size. The particles can have a substantially monodispersesize distribution or a polymodal distribution obtained by blending twoor more substantially monodisperse distributions. The inorganic oxideparticles are typically non-aggregated (substantially discrete), asaggregation can result in precipitation of the inorganic oxide particlesor gelation of the hardcoat. The inorganic oxide particles are typicallycolloidal in size, having an average particle diameter of about 0.001 toabout 0.2 micrometers, less than about 0.05 micrometers, and less thanabout 0.03 micrometers. These size ranges facilitate dispersion of theinorganic oxide particles into the binder resin and provide ceramerswith desirable surface properties and optical clarity. The averageparticle size of the inorganic oxide particles can be measured usingtransmission electron microscopy to count the number of inorganic oxideparticles of a given diameter. The inorganic oxide particles can consistessentially of or consist of a single oxide such as silica, or cancomprise a combination of oxides, such as silica and aluminum oxide, ora core of an oxide of one type (or a core of a material other than ametal oxide) on which is deposited an oxide of another type. Silica is acommon inorganic particle. The inorganic oxide particles are oftenprovided in the form of a sol containing a colloidal dispersion ofinorganic oxide particles in liquid media. The sol can be prepared usinga variety of techniques and in a variety of forms including hydrosols(where water serves as the liquid medium), organosols (where organicliquids so serve), and mixed sols (where the liquid medium contains bothwater and an organic liquid), e.g., as described in U.S. Pat. No.5,648,407 (Goetz et al.); U.S. Pat. No. 5,677,050 (Bilkadi et al.) andU.S. Pat. No. 6,299,799 (Craig et al.), the disclosure of which isincorporated by reference herein. Aqueous sols (e.g. of amorphoussilica) can be employed. Sols generally contain at least 2 wt-%, atleast 10 wt-%, at least 15 wt-%, at least 25 wt-%, and often at least 35wt-% colloidal inorganic oxide particles based on the total weight ofthe sol. The amount of colloidal inorganic oxide particle is typicallyno more than 50 wt-% (e.g. 45 wt-%). The surface of the inorganicparticles can be “acrylate functionalized” as described in Bilkadi etal. The sols can also be matched to the pH of the binder, and cancontain counterions or water-soluble compounds (e.g., sodium aluminate),all as described in Kang et al. '798.

One example of such particles is colloidal silica reacted with amethacryl silane coupling agent such as A-174 (available from Natrochem,Inc.), other dispersant aids such as N,N dimethylacrylamide and variousother additives (stabilizers, initiators, etc.).

A particulate matting agent can be incorporated into the polymerizablecomposition in order to impart anti-glare properties to the surfacelayer. The particulate matting agent also prevents the reflectancedecrease and uneven coloration caused by interference with an associatedhard coat layer. The particulate matting agent should preferably betransparent, exhibiting transmission values of greater than about 90%.Alternatively, or in addition thereto, the haze value is preferably lessthan about 5%, and more preferably less than about 2%, and mostpreferably less than about 1%.

Exemplary systems incorporating matting agents into a hard coatinglayer, but having a different hard coating composition, are described,for example, in U.S. Pat. No. 6,693,746, and herein incorporated byreference. Further, exemplary matte films are commercially availablefrom U.S.A. Kimoto Tech of Cedartown, Ga., under the trade designation“N4D2A.”

The amount of particulate matting agent added is between about 0.5 and10% of the total solids of the composition, depending upon the thicknessof the layer 18, with a preferred amount around 2%. The anti-glare layer18 preferably has a thickness of 0.5 to 10 microns, more preferably 0.8to 7 microns, which is generally in the same thickness range of glosshard coatings.

The average particle diameter of the particulate matting agent has apredefined minimum and maximum that is partially dependent upon thethickness of the layer. However, generally speaking, average particlediameters below 1.0 microns do not provide the degree of anti-glaresufficient to warrant inclusion, while average particle diametersexceeding 10.0 microns deteriorate the sharpness of the transmissionimage. The average particle size is thus preferably between about 1.0and 10.0 microns, and more preferably between 1.7 and 3.5 microns, interms of the number-averaged value measured by the Coulter method.

As the particulate matting agent, inorganic particles or resin particlesare used including, for example, amorphous silica particles, TiO₂particles, Al₂O₃ particles, cross-linked acrylic polymer particles suchas those made of cross-linked poly(methyl methacrylate), cross-linkedpolystyrene particles, melamine resin particles, benzoguanamine resinparticles, and cross-linked polysiloxane particles. By taking intoaccount the dispersion stability and sedimentation stability of theparticles in the coating mixture for the anti-glare layer and/or thehard coat layer during the manufacturing process, resin particles aremore preferred, and in particular cross-linked polystyrene particles arepreferably used since resin particles have a high affinity for thebinder material and a small specific gravity.

As for the shape of the particulate matting agent, spherical andamorphous particles can be used. However, to obtain a consistentanti-glare property, spherical particles are desirable. Two or morekinds of particulate materials may also be used in combination.

Other types of inorganic particles can be incorporated into the hardcoats of this invention. Particularly preferred are conducting metaloxide nanoparticles such as antimony tin oxide, fluorinated tin oxide,vanadium oxide, zinc oxide, antimony zinc oxide, and indium tin oxide.They can also be surface treated with materials such as3-methacryloxypropyltrimethoxysilane. These particles can provideconstructions with antistatic properties. This is desirable to preventstatic charging and resulting contamination by adhesion of dust andother unwanted debris during handling and cleaning of the film.Preferably, such metal oxide particles are incorporated into the top(thin) layer of the two-layer constructions of this invention, in whichthe fluorinated hardcoat is applied to a hydrocarbon-based hardcoat. Atthe levels at which such particles may be needed in the coating in orderto confer adequate antistatic properties (typically 25 wt % andgreater), these deeply colored particles can impart undesired color tothe construction. However, in the thin top layer of a two-layerfluorinated hardcoat construction, their effect on the optical andtransmission properties of the film is minimized Examples of conductingmetal oxide nanoparticles useful in this embodiment include antimonydouble oxide available from Nissan Chemical under the trade designationsCelnax CXZ-210IP and CXZ-210IP-F2. When these particles are included atappropriate levels in the coatings of this invention, the resultingfluorinated hardcoats can exhibit static charge decay times less thanabout 0.5 sec. In this test, the sample is placed between two electricalcontacts and charged to +/−5 kV. The sample is then grounded, and thetime necessary for the charge to decay to 10% of its initial value ismeasured and recorded as the static charge decay time. In contrast, filmconstructions containing no conducting nanoparticles exhibit staticcharge decay times >30 sec.

Thin coating layers 18 of any of the preferred embodiments can beapplied to the optical substrate 16 using a variety of techniques,including dip coating, forward and reverse roll coating, wire wound rodcoating, and die coating. Die coaters include knife coaters, slotcoaters, slide coaters, fluid bearing coaters, slide curtain coaters,drop die curtain coaters, and extrusion coaters among others. Many typesof die coaters are described in the literature such as by Edward Cohenand Edgar Gutoff, Modern Coating and Drying Technology, VCH Publishers,NY 1992, ISBN 3-527-28246-7 and Gutoff and Cohen, Coating and DryingDefects: Troubleshooting Operating Problems, Wiley Interscience, NY ISBN0-471-59810-0.

A die coater generally refers to an apparatus that utilizes a first dieblock and a second die block to form a manifold cavity and a die slot.The coating fluid, under pressure, flows through the manifold cavity andout the coating slot to form a ribbon of coating material. Coatings canbe applied as a single layer or as two or more superimposed layers.Although it is usually convenient for the substrate to be in the form ofa continuous web, the substrate may also be a succession of discretesheets.

To prove the effectiveness of the hard coat formulations according toeach preferred embodiment of the present invention described above,sample hard coats having the given compositions were formulated andapplied to PET substrates and compared to hard coat formulations havingless than all the desired components. The coatings were visuallyinspected and tested for ink repellency, durability and surfaceroughness. The experimental procedures and tabulated results aredescribed below:

I. Experimental Procedures:

A: Ingredients

Unless otherwise noted, as used in the examples, “HFPO-” refers to theend group F(CF(CF₃)CF₂O)_(a)CF(CF₃)— of the methyl esterF(CF(CF₃)CF₂O)aCF(CF₃)C(O)OCH₃ wherein a averages about 6.22, with anaverage molecular weight of 1,211 g/mol, can be prepared according tothe method reported in U.S. Pat. No. 3,250,808 (Moore et al.), thedisclosure of which is incorporated herein by reference, withpurification by fractional distillation.

Polyisocyanates Desmodur™ (Des) N100, Desmodur™ 3300, Desmodur™TPLS2294, Desmodur™ N 3600, and Isophorone diisocyanate (IPDI) wereobtained from Bayer Polymers LLC, of Pittsburgh, Pa.

PAPI (Poly[(phenyl isocyanate)-co-formaldehyde]) (MW about 375), isavailable from Sigma Aldrich of Milwaukee, Wis.

C₆F₁₃C₂H₄OH is available from Sigma Aldrich of Milwaukee, Wis.

4-methoxy phenol (MEHQ) is available from Sigma Aldrich of Milwaukee,Wis.

HO(CH₂)₁₀OH is available from Sigma Aldrich of Milwaukee, Wis.

FOX-diol (H(OCH₂CCH₃(CH₂OCH₂CF₃)CH₂)_(x)OH) (MW about 1342), isavailable from Omnova Solutions Inc. of Akron, Ohio.

Pentaerythritol tetraacrylate (“PET4A”), under the trade designation“SR295”, was obtained from Sartomer Company of Exton, Pa.

Pentaerythritol triacrylate (“PET3A”), under the trade designation“SR444C”, was obtained from Sartomer Company of Exton, Pa.

Trimethylolpropane triacrylate (“TMPTA”), under the trade designation“SR351”, was obtained from Sartomer Company of Exton, Pa.

Hydantoin hexaacrylate (HHA) was prepared as described in Example 1 ofU.S. Pat. No. 4,262,072.

FBSEE (C₄F₉SO₂N(C₂H₄OH)₂), a fluorochemical diol, can be prepared asdescribed in column 5, line 31 and in FIG. 9 of U.S. Pat. No. 3,734,962(1973).

MeFBSE (C₄F₉SO₂N(CH₃)CH₂CH₂OH) was prepared by essentially following theprocedure described in U.S. Pat. No. 6,664,354 (Savu et al.), Example 2,Part A.

FBSEA (C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH═CH₂) is made by the procedure ofExamples 2A and 2B of WO 01/30873 to Savu et al.

HFPO-AEA (HFPO—C(O)NHCH₂CH₂OC(O)CH═CH₂) was prepared as described inFile number U.S. Pat. No. 7,101,618; under Preparation of MonofunctionalPerfluoropolyether Acrylate (FC-1). Hereafter its use is noted as 31a.

Fomblin Zdol (HOCH₂CF₂(OCF₂CF₂)_(n)(OCF₂)_(m)CH₂OH) is available fromSolvay Solexis, Inc. of Italy.

LTM diacrylate,CH₂═CHC(O)OCH₂CF₂O(CF₂CF₂O)_(mm)(CF₂O)_(nn)CH₂OC(O)CH═CH₂, was preparedfrom Fomblin Zdol according to the procedure of Example XV of U.S. Pat.No. 3,810,874.

Hydroxyethyl acrylate (HEA) is available from Sigma Aldrich ofMilwaukee, Wis.

H₂NCH₂CH₂CH₂Si(OCH₃)₃ is available from Sigma Aldrich of Milwaukee, Wis.

HSCH₂CH₂CH₂Si(OCH₃)₃ is available from Sigma Aldrich of Milwaukee, Wis.

2-isocyanato-ethyl methacrylate (“IEM”) (CH₂═C(CH3)CO₂CH₂CH₂NCO), isavailable from Sigma Aldrich of Milwaukee, Wis.

CN 4000 is available from Sartomer Company of Exton, Pa. It is an α,ωdifunctional perfluoropolyether oligomer with 55% wt fluorine and amolecular weight of approximately 2000 g/mol.

The amines, triethylamine, 2-amino-2-ethyl-1,3-propanediol, and1,1-bis-(hydroxyethyl)-1,3 aminopropane were obtained from Sigma-Aldrichof Milwaukee, Wis.

Acryloyl chloride was obtained from Sigma-Aldrich of Milwaukee Wis.

The UV photoinitiator, 1-hydroxycyclohexyl phenyl ketone used wasobtained from Ciba Specialty Products, Tarrytown, N.Y. and sold underthe trade designation “Irgacure 184.”

The photoinitiator2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one used wasobtained from Ciba Specialty Products, Tarrytown, N.Y. and sold underthe trade designation “Irgacure 907.”

Methyl perfluorobutyl ether (HFE 7100) was obtained from 3M Company, St.Paul, Minn.

Dibutyltin dilaurate (DBTDL) was obtained from Sigma Aldrich ofMilwaukee, Wis.

B. Preparation of Experimental Materials

Unless otherwise noted, “MW” refers to molecular weight and “EW” refersto equivalent weight. Further, “° C.” may be used interchangeably with“degrees Celsius” and “mol” refers to moles of a particular material and“eq” refers to equivalents of a particular material. Further, “Me”constitutes a methyl group and may be used interchangeably with “CH₃.”

Preparation No. 1. Preparation of HFPO—C(O)OCH₃

As used in the examples, “HFPO-” refers to the end groupF(CF(CF₃)CF₂O)_(a)CF(CF₃)— wherein a has average values of about 4.41,6.2, 6.85, and 8.07. The material F(CF(CF₃)CF₂O)_(a)CF(CF₃)COOCH₃(HFPO—C(O)OCH₃) can be prepared according to the method reported in U.S.Pat. No. 3,250,808 (Moore et al.), the disclosure of which isincorporated herein by reference, with purification by fractionaldistillation.

Preparation No. 2. Preparation of HFPO DiolHFPO—C(O)NHCH₂CH₂CH₂N(CH₂CH₂OH)₂ (HFPODO, MW about 1341)

To a 500 ml 3-necked flask equipped with a stir bar and reflux condenserwas charged 100 g (MW about 1210.6, 0.0826 mol) HFPO—C(O)OCH₃, and 13.40g (MW=162.2, 0.0826 mol) H₂NCH₂CH₂CH₂N(CH₂CH₂OH)₂. The mixture wasreacted neat at 130 degrees Celsius for 6 hours. From Fourier TransformInfrared Spectroscopy (FTIR) analysis, the amide —C(O)NH— was formed asthe ester signal (—CO₂—) disappeared. The desired product, HFPO—C(O)NHCH₂CH₂CH₂N(CH₂CH₂OH)₂ was obtained as a viscous yellow liquid afterconcentration at 55 degrees Celsius under aspirator vacuum.

Preparation No. 3. Preparation of HFPO—C(O)N(H)C(CH₂OH)₂CH₂CH₃ StartingMaterial

To a 500 ml 3-necked flask equipped with a stir bar and reflux condenserwas charged 11.91 g (0.1 mol) H₂NC(CH₂OH)₂CH₂CH₃ and 60 gtetrahydrofuran (“THF”). Next via dropping funnel was added 121.1 g (0.1mol) HFPO—C(O)OCH₃ over about 80 minutes at a bath temperature of about85 degrees Celsius. The reaction was cloudy at first, but became clearabout 1 hour into the reaction. After addition was complete, the heatingbath was shut off and the reaction was allowed to cool for three days.The material was concentrated at 55 degrees Celsius under aspiratorvacuum to yield 130.03 g of a light colored syrup. NMR analysis showedthe product to be an 87:13 mixture of the structures I and II asfollows:

Preparation No. 4a. Preparation of HFPO—C(O)NHCH₂CH₂OH

HFPO—C(O)N(H)CH₂CH₂OH of different molecular weights (938.5, 1344, and1547.2) were made by a procedure similar to that described in U.S. Pat.No. 7,094,829, with the exception that F(CF(CF₃)CF₂O)_(a)CF(CF₃)C(O)CH₃with a=6.2 was replaced with F(CF(CF₃)CF₂O)_(a)CF(CF₃)C(O)OCH₃ whereina=4.41, 6.85, and 8.07 respectively.

Preparation No. 4b, Synthesis of HFPOC(O)—NH—CH₂CH₂—O—CH₂CH₂—OCH₂CH₂—OHStarting Material (i.e. HFPO-EO3-OH)HFPO—C(O)OCH₃

(Mw=1340 g/mole. 100.0 g) was placed in a 500 ml round bottom flask. Theflask was purged with nitrogen and placed in a water bath to maintain atemperature of 50° C. or less. To this flask was added 9.5 g (0.091 mol)of 2-aminoethoxyethoxyethanol (obtained from Huntsman Chemicals ofAustin, Tex. as XTA-250.) The reaction mixture was observed to beinitially two phases, but with stirring, it gradually turned lightyellow and homogenized within about 30 min. The reaction mixture wasallowed to stir for 48 hrs. After this time an infrared spectrum of thereaction mixture showed complete loss of the methyl ester band at 1780cm⁻¹ and the presence of the strong amide carbonyl stretch at 1718 cm⁻¹.Methyl t-butyl ether (200 ml) was added to the reaction mixture and theorganic phase was extracted twice with water/HCl (˜15%) to removeunreacted amine and methanol. The MTBE layers were combined and driedwith MgSO₄. The MTBE was removed under reduced pressure to yield aclear, viscous liquid. Further drying at 0.1 mm Hg at room temperaturefor 16 hrs, resulted in 101.3 g (90% yield). ¹H NMR and IR spectroscopyconfirmed the formation of the above-identified compound HFPO-EO3-OH.

Preparation No. 4c, Synthesis ofHFPOC(O)—NH—CH₂CH₂—O—CH₂CH₂—O—CH₂CH₂O—CH₂CH₂O—OH Starting Material (i.e.HFPO-EO4-OH)

The same synthetic process was used for the preparation of HFPO-EO4-OHas the EO3-OH adduct except the starting amino-EO4-alcohol,aminoethoxyethoxyethoxy ethanol was used instead of amino EO3.EO4-alcohol was obtained from Huntsman Chemicals of Austin, Tex. asXTA-350.

Preparation No. 4d, Synthesis of HFPOC(O)—NH—(CH₂)₆—OH Starting Material(i.e. HFPO-AH-OH)

The same synthetic procedure was used for the preparation of HFPO-AH-OHas the EO3-OH adduct except the starting aminoalcohol was6-amino-hexanol available from Aldrich Chemical Co. Milwaukee, Wis.

C. General Procedure-Synthesis of Perfluoropolyether UrethaneMultiacrylate

Preparation No. 5. Preparation of Des N100/0.66 PET3A/0.33 HFPO

A 500 ml roundbottom flask equipped with magnetic stir bar was chargedwith 25.0 g (0.131 eq, 191 EW) Des N100, 43.13 g (0.087 eq, 494.3 EW) ofSartomer SR444C, 25.3 mg of MEHQ, and 126.77 g methyl ethyl ketone(MEK). The reaction was swirled to dissolve all the reactants, the flaskwas placed in a oil bath at 60 degrees Celsius, and fitted with acondenser under dry air. Two drops of dibutyltin dilaurate was added tothe reaction. After 1 hour, 58.64 g (0.0436 eq, 1344 EW)F(CF(CF₃)CF₂O)_(6.85)CF(CF₃)C(O)NHCH₂CH₂OH was added to the reaction viaaddition funnel over about 75 minutes. The reaction was monitored byFTIR and showed a small isocyanate absorption at 2273 cm⁻¹ after about 5hours of reaction, but no isocyanate absorption at 7.5 hours ofreaction. The material was used as a 50% solids solution in MEK. TheHFPO multiacrylate urethanes preparations shown in Table 1 below, listedas Preparation Nos. 5.1 through 5.19 respectively, were all madeaccording to this general procedure, using the appropriate molefractions of materials noted in the table.

TABLE 1 Perfluoropolyether Urethane Multiacrylates Isocyanate used (setat 100 Mole Mole Preparation percent NCO percent Number in all casesPET3A Mole percent HFPO- C(O)NHCH₂CH₂OH (MW 1344) 5.1 Des N100 95 5 5.2Des N100 85 15 5.3 Des N100 75 25 5.4 Des N100 66.6 33.3 5.5 Des N100 5050 5.6 Des N100 33.3 66.6 5.7 Des N100 5 95 5.8 Des N3300 85 15 5.9 DesN3300 75 25 5.10 Des N3300 66.6 33.3 5.11 Des N3300 50 50 5.12 IPDI 7525 5.13 Des TPLS2294 85 15 5.14 Des N3600 85 15 Mole percentHFPO-C(O)NH(CH₂)₃NHCH₃ (See Preparation number 22) 5.15 Des N100 85 15Mole percent HFPO- C(O)NHCH₂CH₂OH (MW 938.5) 5.16 Des N100 85 15 5.17Des N100 75 25 Mole percent HFPO- C(O)NHCH₂CH₂OH (MW 1547.2) 5.18 DesN100 85 15 5.19 Des N100 75 25Preparation No. 6. Preparation of Des N100/0.90 PET3A/0.15 HFPO

A 500 ml roundbottom 2-necked flask equipped with magnetic stir bar wascharged with 25.00 g (0.131 eq, 191 EW) Des N100, 26.39 g (0.0196 eq,1344 EW) F(CF(CF₃)CF₂O)_(6.85) CF(CF₃)C(O)NHCH₂CH₂OH, and 109.62 g MEK,and was swirled to produce a homogeneous solution. The flask was placedin an 80 degrees Celsius bath, charged with 2 drops of dibutyltindilaurate catalyst, and fitted with a condenser. The reaction was cloudyat first, but cleared within two minutes. At about 1.75 hours, the flaskwas removed from the bath and 2.42 g of MEK was added to compensate forlost solvent. A 2.0 g sample was removed from the flask, leaving(1-(2.0/161.01) or 0.9876 weight fraction, of the reaction, and 57.51 g(98.76% of 58.23 g) (0.116 mol, 494.3 equivalent weight) PET3A was addedto the reaction, which was placed in a 63 degrees Celsius bath. At about5.25 hours FTIR showed no isocyanate absorption at 2273 cm⁻¹, and 0.56 gMEK was added to compensate for solvent lost to bring the material to50% solids. The product has a calculated wt % F of 15.6%).

Preparation No. 7. Preparation of Des N100/0.90 HEA/0.10 HFPO

By a procedure similar to that for Preparation 5.1 shown in Table 1above, 28.34 g (0.1484 eq) Des N100, 19.94 g (0.148 eq) F(CF(CF₃)CF₂O)_(6.85) CF(CF₃)C(O)NHCH₂CH₂OH, in 63.8 g MEK, with 2 drops ofDBTDL, 0.03 g BHT were reacted for 1 hour, followed by addition of 15.51g (0.1336 eq) HEA to provide, after reaction overnight, the desiredmaterial.

Preparation No. 8. Preparation of DesN100/HFPO—C(O)NHCH₂CH₂OH/MeFBSE/PET3A (in 30/10/10/10 Ratio):

A 120 ml bottle was charged with 5.73 g Des N100 (EW about 191, about 30milliequivalents NCO), 3.57 g MeFBSE (MW=357, 10 milliequivalents OH),13.44 g HFPO—C(O)NHCH₂CH₂OH (MW about 1344, 10 milliequivalents OH),4.94 g PET3A (EW about 494.3, about 10 milliequivalents OH), 5 drops ofdibutyltin dilaurate catalyst and 42 g MEK (about 40% solid) undernitrogen. The solution was reacted at 70 degrees Celsius in an oil bathwith a magnetic stir bar for 20 hours after sealing the bottle. A clearsolution was obtained after reaction, which showed no unreacted —NCOsignal in FTIR analysis.

Preparation No. 9. Preparation of DesN100/HFPO—C(O)NHCH₂CH₂OH/MeFBSE/PET3A (in 40/10/10/20 Ratio):

A 120 ml bottle was charged with 7.64 g Des N100 (EW about 191, about 40milliequivalents NCO), 3.57 g MeFBSE (MW=357, 10 milliequivalents OH),13.44 g HFPO—C(O)NHCH₂CH₂OH (MW about 1344, 10 milliequivalents OH),9.89 g PET3A (EW about 494.3, about 20 milliequivalents OH), 5 drops ofdibutyltin dilaurate catalyst and 52 g MEK (about 40% solid) undernitrogen. The solution was reacted at 70 degrees Celsius in an oil bathwith a magnetic stir bar for 20 hours after sealing the bottle. A clearsolution was obtained after reaction, which showed no unreacted —NCOsignal in FTIR analysis.

Preparation No. 10. Preparation of Des 100/C₆F₁₃C₂H₄OH/PET3A (in20/10/10 Ratio)

A 120 ml bottle was charged with 3.82 g Des N100 (EW about 191, about 20milliequivalents NCO), 3.64 g C₆F₁₃C₂H₄OH (MW=363, 10 milliequivalentsOH), 4.94 g PET3A (EW about 494.3, about 10 milliequivalents OH), 3drops of dibutyltin dilaurate catalyst and 19 g MEK (about 40% solid)under nitrogen. The solution was reacted at 70 degrees Celsius in an oilbath with a magnetic stir bar for 20 hours after sealing the bottle. Aclear solution was obtained after reaction, which showed no unreacted—NCO signal in FTIR analysis.

Preparation No. 11. Preparation of Des100/HO(CH₂)₁₀OH/HFPO—C(O)NHCH₂CH₂OH/PET3A (in 60/20/15/25 Ratio)

A 120 ml bottle was charged with 11.46 g Des N100 (EW about 191, about60 milliequivalents NCO), 1.74 g HO(CH₂)₁₀OH (MW=174, 20milliequivalents OH), 20.16 g HFPO—C(O)NHCH₂CH₂OH (MW about 1344, 15milliequivalents OH), 12.36 g PET3A (EW about 494.3, about 25milliequivalents OH), 5 drops of dibutyltin dilaurate catalyst and 106 gMEK (about 30% solid) under nitrogen. The solution was reacted at 70degrees Celsius in an oil bath with a magnetic stir bar for 20 hoursafter sealing the bottle. A clear solution was obtained after reaction,which showed no unreacted —NCO signal in FTIR analysis.

Preparation No. 12. Preparation of DesN100/FBSEE/HFPO—C(O)NHCH₂CH₂OH/PET3A (in 30/10/7.5/12.5 Ratio)

A 120 ml bottle was charged with 5.73 g Des N100 (EW about 191, about 30milliequivalents NCO), 1.94 g FBSEE (MW=387, 10 milliequivalents OH),10.08 g HFPO—C(O)NHCH₂CH₂OH (MW about 1344, 7.5 milliequivalents OH),6.18 g PET3A (EW about 494.3, about 12.5 milliequivalents OH), 5 dropsof dibutyltin dilaurate catalyst and 56 g MEK (about 30% solid) undernitrogen. The solution was reacted at 70 degrees Celsius in an oil bathwith a magnetic stir bar for 20 hours after sealing the bottle. A clearsolution was obtained after reaction, which showed no unreacted —NCOsignal in FTIR analysis.

Preparation No. 13. Preparation of Des N3300/HFPODO/PET3A (in 30/10/20Ratio)

A 240 ml bottle was charged with 5.79 g Des N3300 (EW about 193, about30 milliequivalents NCO), 6.71 g HFPODO (MW about 1341, 10milliequivalents OH), 9.89 g PET3A (EW about 494.3, about 20milliequivalents OH), 5 drops of dibutyltin dilaurate catalyst and 52 gMEK (about 30% solid) under nitrogen. The solution was reacted at 70degrees Celsius in an oil bath with a magnetic stir bar for 10 hoursafter sealing the bottle. There was a small amount of precipitate formedupon standing at room temperature. FTIR analysis showed no unreacted—NCO signal.

Preparation No. 14. Preparation of DesN3300/HFPODO/HFPO—C(O)NHCH₂CH₂OH/PET3A (in 30/10/5/15 Ratio)

A 240 ml bottle was charged with 5.79 g Des N3300 (EW about 193, about30 milliequivalents NCO), 6.71 g HFPODO (MW about 1341, 10milliequivalents OH), 6.72 g HFPO—C(O)NHCH₂CH₂OH (MW about 1344, 5milliequivalents OH), 7.42 g PET3A (EW about 494.3, about 15milliequivalents OH), 5 drops of dibutyltin dilaurate catalyst, 27 g MEKand 10 g C₄F₉OCH₃ (about 20% solid) under nitrogen. The solution wasreacted at 70 degrees Celsius in an oil bath with a magnetic stir barfor 10 hours after sealing the bottle. Separation into two liquid phasesoccurred upon standing at room temperature. Addition of more C₄F₉OCH₃produced a clear homogeneous solution at about 17% solids. FTIR analysisshowed no unreacted —NCO signal.

Preparation No. 15. Preparation of Des N3300/HFPODO/MeFBSE/PET3A (in30/10/5/15 Ratio)

A 120 ml bottle was charged with 5.79 g Des N3300 (EW about 191, about30 milliequivalents NCO), 6.71 g HFPODO (MW about 1341, 10milliequivalents OH), 1.79 g MeFBSE (MW=357, 5 milliequivalents OH),7.42 g PET3A (EW about 494.3, about 15 milliequivalents OH), 5 drops ofdibutyltin dilaurate catalyst and 51 g MEK (about 30% solid) undernitrogen. The solution was reacted at 70 degrees Celsius in an oil bathwith a magnetic stir bar for 10 hours after sealing the bottle. A clearsolution was obtained at 70 degrees Celsius after reaction, but therewas a small amount of precipitate formed upon standing at roomtemperature. FTIR analysis showed no unreacted —NCO signal.

Preparation No. 16. Preparation of DesN3300/Fox-Diol/HFPO—C(O)NHCH₂CH₂OH/PET3A (in 30/10/5/15 Ratio)

A 240 ml bottle was charged with 5.79 g Des N3300 (EW about 191, about30 milliequivalents NCO), 6.71 g Fox-Diol (MW about 1341, 10milliequivalents OH), 6.72 g HFPO—C(O)NHCH₂CH₂OH (MW about 1344, 5milliequivalents OH), 7.40 g PET3A (EW about 494.3, about 15milliequivalents OH), 5 drops of dibutyltin dilaurate catalyst, 56 g MEKand 50 g C₄F₉OCH₃ (about 19% solid) under nitrogen. The solution wasreacted at 70 degrees Celsius in an oil bath with a magnetic stir barfor 10 hours after sealing the bottle. A clear solution was obtainedafter reaction. FTIR analysis showed no unreacted —NCO signal.

Preparation No. 17. Preparation of Des N3300/Fomblin Zdol/PET3A (in30/10/20 Ratio)

A 240 ml bottle was charged with 5.79 g Des N3300 (EW about 191, about30 milliequivalents NCO), 10.0 g Fomblin Zdol (MW about 2000, 10milliequivalents OH), 9.89 g PET3A (EW about 494.3, about 20milliequivalents OH), 5 drops of dibutyltin dilaurate catalyst, 63 g MEKand 40 g C₄F₉OCH₃ (about 18% solid) under nitrogen. The solution wasreacted at 70 degrees Celsius in an oil bath with a magnetic stir barfor 10 hours after sealing the bottle. A clear solution was obtainedafter reaction. FTIR analysis showed no unreacted —NCO signal.

Preparation No. 18. Preparation of DesN3300/HHA/HFPO—C(O)NHCH₂CH₂OH/PET3A (in 30/10/10/10 Ratio)

A 240 ml bottle was charged with 5.79 g Des N3300 (EW about 191, about30 milliequivalents NCO), 6.14 g HHA (MW about 1228, 10 milliequivalentsOH), 12.29 g HFPO—C(O)NHCH₂CH₂OH (MW about 1229, 10 milliequivalentsOH), 4.93 g PET3A (EW about 494.3, about 10 milliequivalents OH), 5drops of dibutyltin dilaurate catalyst, 85 g MEK and 25 g C₄F₉OCH₃(about 20% solid) under nitrogen. The solution was reacted at 70 degreesCelsius in an oil bath with a magnetic stir bar for 10 hours aftersealing the bottle. A clear solution was obtained after reaction. FTIRanalysis showed no unreacted —NCO signal.

Preparation No. 19. Preparation of PAPI/HFPO—C(O)NHCH₂CH₂OH/PET3A (in28/8/20 Ratio)

A 120 ml bottle was charged with 3.75 g PAPI (EW about 134, about 28milliequivalents NCO), 10.75 g HFPO—C(O)NHCH₂CH₂OH (MW about 1344, 8milliequivalents OH), 9.88 g PET3A (EW about 494.3, about 20milliequivalents OH), 5 drops of dibutyltin dilaurate catalyst and 37 gMEK (about 40% solid) under nitrogen. The solution was reacted at 70degrees Celsius in an oil bath with a magnetic stir bar for 5 hoursafter sealing the bottle. A clear solution was obtained after reaction.FTIR analysis showed no unreacted —NCO.

D. General Preparation of Perfluoropolyether Urethane MultiacrylatesContaining Trialkoxysilane Functionality.

Preparation No. 20. Preparation of Des N100/0.75 PET3A/0.15 HFPO/0.15H₂N(CH₂)₃Si(OCH₃)₃

A 500 ml roundbottom flask equipped with stir bar was charged with 25.00g (0.1309 eq) Des N100, 103.43 g MEK, 2 drops of DBTDL, 26.39 g (0.0196eq) HFPO—C(O)NHCH₂CH₂OH, 1344 equivalent weight, and 0.05 g BHT, andplaced in a 60 degrees Celsius oil bath. After 1 hour, 3.52 g (0.0196eq) H₂N(CH₂)₃Si(OCH₃)₃ was added, followed in 10 minutes by the additionof 48.52 g (0.0982 eq, 494.3 equivalent weight) SR444C. The reactionmixture showed no residual isocyanate by FTIR after a total reactiontime of 5.75 hours.

The preparation of other perfluoropolyether urethane multiacrylatescontaining trialkoxysilane functionality was done by a similarprocedure, substituting the appropriate amounts of materials, and aresummarized in Table 2 as Preparation Nos. 20.1 through 20.4:

TABLE 2 Isocyanate used (set at 100 Mole Mole Mole percent Preparationpercent NCO in percent HFPO- Mole percent Number all cases) PET3AC(O)NHCH₂CH₂OH H₂N(CH)₂)₃•Si(OCH₃)₃ 20.1 Des N100 75 15 15 20.2 Des N10060 15 30 20.3 Des N100 45 15 45 20.4 Des N100 30 15 60Preparation No. 21. Preparation of DesN3300/HFPO—C(O)NHCH₂CH₂OH/HSC₃H₆Si(OCH₃)₃/PET3A (in 30/8/2/20 Ratio)

A 240 ml bottle was charged with 5.79 g Des N3300 (EW about 193, about30 milliequivalents NCO), 9.83 g HFPO—C(O)NHCH₂CH₂OH (MW about 1229, 8milliequivalents OH), 0.39 g HSC₃H₆Si(OMe)₃ (MW=196, 2 milliequivalentsSH), 5 drops of dibutyltin dilaurate catalyst, 40 g MEK and 20 gC₄F₉OCH₃ under nitrogen. The solution was reacted at 70 degrees Celsiusin an oil bath with a magnetic stir bar for 2 hours after sealing thebottle. Then, 4.46 g PET3A (EW about 494.3, about 20 milliequivalentsOH) was added at room temperature under nitrogen. The solution wasallowed to react for another 6 hours at 70 degrees Celsius. A clearsolution was obtained after reaction, which showed no unreacted —NCOsignal in FTIR analysis.

Preparation No. 22. Preparation of HFPO—C(O)NHCH₂CH₂CH₂NHCH₃ StartingMaterial

A 1-liter round-bottom flask was charged with 291.24 g (0.2405 mol) ofHFPO—C(O)OCH₃ and 21.2 g (0.2405 mol)N-methyl-1,3-propanediamine, bothat room temperature, resulting in a cloudy solution. The flask wasswirled and the temperature of the mixture rose to 45 degrees Celsius,and to give a water-white liquid, which was heated overnight at 55degrees Celsius. The product was then placed on a rotary evaporator at75 degrees Celsius and 28 inches of Hg vacuum to remove methanol,yielding 301.88 g of a viscous slightly yellow liquid, nominal molecularweight is equal to 1267.15 g/mol.

Preparation No. 23. Preparation of HFPO—C(O)NHC(CH₂CH₃)(CH₂OC(═O)NHC₂H₄OC(O)C(CH₃)═CH₂)₂

A 240 ml bottle was charged with 6.49 g HFPO—C(O)NHC(CH₂CH₃)(CH₂OH)₂(1298.5 MW, 5 mmol) (“Preparation No. 3”), 1.55 g IEM(OCNC₂H₄OC(O)C(CH₃)═CH₂, MW=155, 10 mmol), 3 drops of dibutyltindilaurate catalyst, 50 mg BHT, 32 g ethyl acetate and 10 g C₄F₉OCH₃. Thesolution was reacted at 70 degrees Celsius in an oil bath with amagnetic stir bar for 8 hours after sealing the bottle. A clear solutionwas obtained after reaction, which showed no unreacted —NCO by in FTIRanalysis, providing a solution of the product HFPO—C(O)NHC(CH₂CH₃)(CH₂OC(═O)NHC₂H₄OC(O)C(CH₃)═CH₂)₂.

Preparation No. 24. Preparation of HFPO—C(O)NHCH₂CH₂OC(═O)NHC₂H₄OC(O)C(CH₃)═CH₂) (HFPO-IEM)

A 120 ml bottle was charged with 71.20 g (MW˜1229, 57.9 mmol)HFPO—C(O)NHC₂H₄OH, 9.0 g of CH₂═C(CH₃)CO₂C₂H₄NCO (MW=155, 58 mmol), 52 gEtOAc, 3 drops of DBTDL and 1.5 mg of phenothiazine under nitrogen. Thesolution was heated in a oil bath at 70 degrees Celsius for 6 hours witha magnetic stirring after sealing the bottle. Fourier Transform InfraredSpectroscopy (FTIR) analysis indicated no remaining isocyanate.

Preparation No. 25. Preparation ofHFPO—C(O)N(H)CH₂CH(OC(O)CH═CH₂)CH₂OC(O)CH═CH₂

The title material was prepared as described in U.S. Patent ApplicationPublication No. 2005/0249940, referred to as FC-4 and had a calculatedwt-% fluorine of 58.5%.

Preparation No. 26. Preparation ofCH₃(O)CCF(CF₃)(OCF₂CF(CF₃)_(b)OCF₂CF₂CF₂CF₂O(CF(CF₃)CF₂O)_(c)CF(CF₃)COOCH₃(H₃CO(O)C— HFPO—C(O)OCH₃)H₃CO(O)C— HFPO—C(O)OCH₃, in which b+c averageabout 4.5 can be prepared using FC(O)CF₂CF₂C(O)F as an initiatoraccording to the method reported in U.S. Pat. No. 3,250,807 (Fritz, etal.) which provides the HFPO oligomer bis-acid fluoride, followed bymethanolysis and purification by removal of lower boiling materials byfractional distillation as described in U.S. Pat. No. 6,923,921 (Flynn,et. al.). The disclosure of both aforementioned patents are incorporatedherein by reference.

Preparation No. 27. Preparation ofHOCH₂CH₂N(H)(O)C—HFPO—C(O)N(H)CH₂CH₂OH

A 200 ml roundbottom flask equipped with magnetic stirbar was chargedwith 3.81 g (0.0624 mol) ethanolamine and heated to 75 degrees Celsiusunder a dry air. A charge of 30.0 g (0.240 mol, 1250 MW) H₃CO(O)C—HFPO—C(O)OCH₃ was added via a pressure equalizing funnel over 40 min andthe reaction was allowed to heat for about 18 h. From Fourier TransformInfrared Spectroscopy (FTIR) analysis, the amide —C(O)NH— was formed asthe ester signal (—CO₂—) disappeared. Next 50.7 g of methyl t-butylether was added to the reaction to provide a solution that was washedsuccessively with 20 ml of 2N aqueous HCl, and then 3 times with 20 mlof water, The solution was then dried over anhydrous magnesium sulfate,filtered and concentrated on a rotary evaporator at aspirator pressurein a 75 degrees Celsius water bath to provide the product as a thicksyrup.

Preparation No. 28. Preparation ofH₂C═CHC(O)OCH₂CH₂N(H)(O)C—HFPO—C(O)N(H)CH₂CH₂OC(O)CH═CH₂

A 500 ml roundbottom equipped with stirbar was charged with 40.00 g(0.0306 mol, 1308.6 MW) HOCH₂CH₂N(H)(O)C—HFPO—C(O)N(H)CH₂CH₂OH, 6.64 g(0.0734 mol) triethylamine, and 54.36 g MTBE and heated at 40 degreesCelsius. A charge of 6.64 g (0.734 mol) of acryloyl chloride was addedvia pressure equalizing funnel over about 30 min, and the reaction wasallowed to heat for about 18 h. The reaction was washed with 40 g 1NHCl, with addition of 60 g of brine and 60 g of MTBE, followed by a washwith 50 g of 5% aqueous sodium carbonate and 50 g of brine, and wasfinally dried over anhydrous magnesium sulfate, filtered andconcentrated on a rotary evaporator at aspirator pressure in a 75degrees Celsius water bath to provide the product as a thick syrup. Ithas a calculated wt-% fluorine of 58.1%.

Preparation No. 29. Preparation of(HOCH₂)₂CH₃CH₂CN(H)(O)C—HFPO—C(O)N(H)CCH₂CH₃(CH₂OH)₂

In a manner similar to the preparation of 27, 65.00 g (0.520 mol)H₃CO(O)C—HFPO—C(O)OCH₃, was reacted with 16.11 g (0.1352 mol)2-amino-2-ethyl-1,3-propanediol to provide after the desired product asa thick slightly yellow syrup.

Preparation No. 30. Preparation of(H₂C═CHC(OOCH₂)₂CH₃CH₂CN(H)(O)C—HFPOC(O)N(H)CCH₂CH₃(CH₂OC(O)CH═CH₂)₂

In a manner similar to the preparation no. 28, 10.00 g (0.0067 mol,1488.3 MW) was dissolved in 16.31 g MTBE and 3.39 g (0.0336 mol)triethylamine, and reacted at 40 degrees Celsius with 2.92 g (0.0323mol) acryloyl chloride, to provide after workup and chromatographicpurification (using 33/67 ethyl acetate/hexane (volume/volume) on aAnalogix™ IF 280 Flash chromatography workstation (Analogix, Inc.,Burlington, Wis.) using a SF40-150 Superflash™ column) the desiredproduct. It has a calculated wt-% fluorine of 50.1%.

Preparation 31a.

HFPO-AEA (HFPO—C(O)NHCH₂CH₂OC(O)CH═CH₂) was prepared as described inU.S. Pat. No. 7,101,618; under Preparation of MonofunctionalPerfluoropolyether Acrylate (FC-1). It has a calculated wt % F of 62.5%.

Preparation 31b. Synthesis of HFPO-EO3-A;

was prepared in a manner similar to HFPO-AEA 31a except the HFPO-amidol,4b (HFPO-EO3-OH) was used in place of 4a. It has a calculated wt % F of59.1%.

Preparation 31c.

Synthesis of HFPO-EO4-A; was prepared in a manner similar to HFPO-AEA31a except the HFPO-amidol, 4c (HFPO-EO4-OH) was used in place of 4a. Ithas a calculated wt % F of 57.4%.

Preparation 31d.

Synthesis of HFPO-AH-A; was prepared in a manner similar to HFPO— AEA31a except the HFPO-amidol, 4d (HFPO-AH-OH) was used in place of 4a. Ithas a calculated wt % F of 60.4%.

E. Test Methods

Steel Wool Testing: The abrasion resistance of the cured films wastested cross-web to the coating direction by use of a mechanical devicecapable of oscillating cheesecloth or steel wool fastened to a stylus(by means of a rubber gasket) across the film's surface. The stylusoscillated over a 10 cm wide sweep width at a rate of 3.5 wipes/secondwherein a “wipe” is defined as a single travel of 10 cm. The stylus hada flat, cylindrical geometry with a diameter of 1.25 inch (3.2 cm). Thedevice was equipped with a platform on which weights were placed toincrease the force exerted by the stylus normal to the film's surface.The cheesecloth was obtained from Summers Optical, EMS Packaging, asubdivision of EMS Acquisition Corp., Hatfield, Pa. under the tradedesignation “Mil Spec CCC-c-440 Product # S12905”. The cheesecloth wasfolded into 12 layers. The steel wool was obtained from Rhodes-American,a division of Homax Products, Bellingham, Washington under the tradedesignation “#0000-Super-Fine” and was used as received. A single samplewas tested for each example, with the weight in grams applied to thestylus and the number of wipes employed during testing reported.

Taber Testing: The Taber test was run according to ASTM D1044-99 usingCS-10 wheels.

Contact Angle: The coatings were rinsed for 1 minute by hand agitationin IPA before being subjected to measurement of water and hexadecanecontact angles. Measurements were made using as-received reagent-gradehexadecane (Aldrich) and deionized water filtered through a filtrationsystem obtained from Millipore Corporation (Billerica, Mass.), on avideo contact angle analyzer available as product number VCA-2500XE fromAST Products (Billerica, Mass.). Reported values are the averages ofmeasurements on at least three drops measured on the right and the leftsides of the drops. Drop volumes were 5 μL for static measurements and1-3 μL for advancing and receding. For hexadecane, only advancing andreceding contact angles are reported because static and advancing valueswere found to be nearly equal.

Surface Smoothness (Dewetting): For some of the tables below, a visualinspection was made regarding the smoothness of the applied dry film.While the measurement of smoothness by visual inspection is a subjectivedetermination, a smooth film, for the purposes of the present invention,is deemed to be a surface layer that is substantially continuous andfree of visible defects in reflected light as observed by visualobservation of the coating surface at a wide variety of possible angles.Typically, visual observation is accomplished by looking at thereflection of a light source from the coating surface at an angle ofabout 60 degrees from perpendicular. Visual defects that may be observedinclude but are not limited to pock marks, fish eyes, mottle, lumps orsubstantial waviness, or other visual indicators known to one ofordinary skill in the art in the optics and coating fields. Thus, a“rough” surface as described below has one or more of thesecharacteristics, and may be indicative of a coating material in whichone or more components of the composition are incompatible with eachother. Conversely, a substantially smooth coating, characterized belowas “smooth” for the purpose of the present invention, presumes to have acoating composition in which the various components, in the reactedfinal state, form a coating in which the components are compatible orhave been modified to be compatible with one another and further haslittle, if any, of the characteristics of a “rough” surface.

The surfaces may also be classified for dewetting as “good,” “veryslight” (v.sl), “slight” (sl), “fair,” or “poor.” A “good” surfacemeaning a substantially smooth surface having little dewetting. A “veryslight,” slight”, or “fair” categorization means that the surface has anincreasing portion of defects but is still substantially acceptable forsmoothness. A “poor” surface has a substantial amount of defects,indicating a rough surface that has a substantial amount of dewetting.

Durability of Ink Repellency was assessed using a modified OscillatingSand Method (ASTM F 735-94). An orbital shaker was used (VWR DS-500E,from VWR Bristol, Conn.). A disk of diameter 89 mm was cut from thesample, placed in a 16 ounce jar lid (jar W216922 from Wheaton,Millville, N.J.), and covered with 50 grams of 20-30 mesh Ottawa sand(VWR, Bristol, Conn.). The jar was capped and placed in the shaker setat 300 rpm for 15 minutes. After shaking, a Sharpie permanent marker wasused to draw a line across the diameter of the disk surface. The portionof the ink line that did not bead up was measured. A measure of 89 mm isequal to 100% ink repellency loss; a measure of 0 mm would be perfectdurability or 0% ink repellency (IR) loss.

F. Experiments

The ceramer hardcoat (“HC-1”) used in the examples was made as describedin column 10, line 25-39 and Example 1 of U.S. Pat. No. 5,677,050 toBilkadi, et al.

Experiment 1:

Solutions as generally described in Tables 3-5 below were prepared at30% solids in a solvent blend of 1:1 isopropanol:ethyl acetate andcoated at a dry thickness of about 4 microns using a number 9 wire woundrod onto 5-mil Melinex 618 film. The coatings were dried in an 80 degreeCelsius oven for 1 minute and then placed on a conveyer belt coupled toa ultraviolet (“UV”) light curing device and UV cured under nitrogenusing a Fusion 500 watt H bulb at 20 ft/min. The values reported in theTables refer to the percent solids of each component of the driedcoating. The coatings were then visually inspected for surfacesmoothness (dewetting). The coatings were also tested for durability ofink repellency. Results are shown in Tables 3 and 4.

TABLE 3 Percentage HC-1 in Preparation Percentage Preparation Inkcoating number in coating Dewet Repel. 99.9 5.5 0.1 good 65 99.8 5.5 0.2v.sl 53 99.7 5.5 0.3 fair 49 99.86 5.4 0.14 sl 51 99.72 5.4 0.28 sl 4499.58 5.4 0.42 sl 40 99.7 5.3 0.3 good 35 99.4 5.3 0.6 v.sl 34 99.1 5.30.9 sl 31 99.9 5.11 0.1 good 65 99.8 5.11 0.2 v.sl 49 99.7 5.11 0.3 sl50 99.86 5.10 0.14 good 60 99.72 5.10 0.28 good 37 99.58 5.10 0.42 v.sl38 99.7 5.9 0.3 good 42 99.4 5.9 0.6 good 43 99.1 5.9 0.9 v.sl 47

Selected coatings, before sand testing, from another coating run wereanalyzed for contact angles and the results are shown in Table 4.

TABLE 4 Preparation Wt % Water static/Adv/Rec Hexadecane Number in HC-1CA (deg) Adv/Rec CA (deg) 5.3 0.3 108/119/91 71/65 5.3 0.6 109/120/9072/67 5.5 1.2 108/120/90 73/67 5.9 1.2 109/121/89 74/67 4.11 1.2108/118/85 74/64

Another set of examples was run according to the same procedure asexamples in Table 1. The results are shown in Table 5.

TABLE 5 Percentage Percentage HC-1 Preparation Preparation Ink incoating number in coating Smoothness Repellency 99.8 5.3 0.2 good 3299.7 5.3 0.3 good 22 99.6 5.3 0.4 v.sl 23 99.76 5.2 0.24 good 46 99.525.2 0.48 good 26 99.33 5.2 0.67 good 42 99.8 5.10 0.2 good 25 99.7 5.100.3 good 42 99.6 5.10 0.4 v.sl 42 99.64 5.9 0.36 good 26 99.43 5.9 0.57good 12 99.22 5.9 0.78 good 33 99.76 5.8 0.24 good 47 99.52 5.8 0.48good 18 99.33 5.8 0.67 v.sl 33

Table 6 shows the results of another set of examples that was run at twolevels of additives in an HC-1 hardcoat in which the sand test was runfor 25 minutes at 300 rpm. The examples were run according to the sameprocedure as examples in Table 1 described above.

TABLE 6 Percentage Percentage HC-1 Preparation Preparation Ink incoating number in coating Smoothness Repellency 99.8 9 0.2 sl 20 99.0 91.0 sl 10 99.8 8 0.2 good 29 99.0 8 1.0 poor 25 99.8 10 0.2 good 38 99.010 1.0 good 30 99.8 11 0.2 good 40 99.0 11 1.0 fair 20 99.8 12 0.2 good36 99.0 12 1.0 poor 22 99.8 19 0.2 good 20 99.0 19 1.0 sl 49 99.8 5.20.2 good 5

Table 7 shows the results of another set of examples that was run at twolevels of additives in an HC-1 hardcoat in which the sand test was runfor 25 minutes at 300 rpm and in a separate set for 35 minutes at 300rpm. The examples were run according to the same procedure as examplesin Table 1 described above.

TABLE 7 Ink Ink % Prep- Percentage Repellency Repellency HC-1 in arationPreparation Smooth- 25 min 35 min coating number in coating ness at 300rpm at 300 rpm 99.5 5.2 0.5 good 0 99.5 5.2 0.5 good 10 99.8 5.1 0.2good 35 99.0 5.1 1.0 good 0 99.0 5.1 1.0 good 36 99.8 5.6 0.2 sl 0 99.05.6 1.0 poor 0 99.8 5.7 0.2 poor 62 99.0 5.7 1.0 poor 26 99.8 5.12 0.2good 0 99.0 5.12 1.0 fair 0 99.8 5.12 0.2 good 54 99.8 5.13 0.2 good 099.0 5.13 1.0 good 0 99.0 5.13 1.0 good 38 99.8 5.14 0.2 good 0 99.05.14 1.0 good 0 99.0 5.14 1.0 good 35 99.8 5.15 0.2 good 5 99.0 5.15 1.0good 0 99.0 5.15 1.0 slight 11 99.8 5.3 0.2 good 0 99.2 5.3 1.0 sl 099.5 5.3 0.5 good 25 99.8 5.16 0.2 good 10 99.0 5.16 1.0 good 0 99.05.16 1.0 good 38 99.8 5.17 0.2 good 0 99.0 5.17 1.0 v.sl 0 99.5 5.17 0.5good 25 99.8 5.18 0.2 good 0 99.0 5.18 1.0 sl 0 99.8 5.18 0.2 good 4799.8 5.19 0.2 good 0 99.0 5.19 1.0 sl 0 99.8 5.19 0.2 sl 36 99.8 8 0.2good 27 98.5 10 1.5 good 30

An example set illustrating the use of perfluoropolyether diols in theinvention was run according to the same procedure as examples inTable 1. These results are shown in Table 8.

TABLE 8 Ink Ink % Percentage repellency repellency HC-1 in PreparationPreparation Smooth- 35 min at 55 min at coating Number in coating ness300 rpm 300 rpm 98.8 13 0.2 good 37 99.0 13 1.0 v.sl 27 99.5 14 0.5 v.sl0 26 99.8 15 0.2 good 34 99.0 15 1.0 v.sl 31 99.8 16 0.2 good 0 28 99.016 1.0 good 0 26 99.8 17 0.2 good 26 99.0 17 1.0 v.sl 34

Another set illustrating the use of a multi acrylate diol in theinvention, and a thiol functional trialkoxysilane was run according tothe same procedure as examples in Table 1. These results are shown inTable 9.

TABLE 9 Percentage Percentage Ink repellency HC-1 in PreparationPreparation 40 min at coating number in coating Smoothness 300 rpm 99.318 0.7 good 32 99.3 21 0.7 good 40 99.3 4.2 0.7 good 0

An example set illustrating the trialkoxysilane functionalperfluoropolyether urethane multiacrylates, a perfluoropolyetherurethane acrylate made using hydroxyethyl acrylate, and aperfluoropolyether diol functionalized with isocyanatoethyl methacrylatewas run according to the same procedure as examples in Table 1. Theseresults are shown in Table 10.

TABLE 10 Ink Percentage Percentage Repellency HC-1 in PreparationPreparation in 20 min at coating Number coating Smoothness 300 rpm 99.620.1 0.4 good 0 99.6 20.2 0.4 good 0 99.6 20.3 0.4 good 0 99.6 20.4 0.4good 0 99.6 7 0.4 good 0 99.6 23 0.4 good 0

A 30% solids (in a solvent blend of 1:1 isopropanol:ethyl acetate)sample of 99.4% PET4A/0.6% Des N100/0.85 PET3A/0.15 HFPO (Preparation5.2) with 2% added Irgacure 907 was prepared. The solution was coatedand cured by the same procedure as above. The smooth coating gave an inkrepellency of 0 after a 20 minute sand test at 300 rpm.

Another set of examples using a perfluoropolyether alcoholfunctionalized with isocyanatoethyl methacrylate in combination with acompatibilizer was run according to the same procedure as examples inTable 1. The results are shown in Table 11.

TABLE 11 Ink Percentage Prep- Percentage Percentage Repellency HC-1 inaration Preparation FBSEA in Smooth- 15 min. at coating Number incoating coating ness 300 rpm 99.7 24 0.03 0 Dewet/ not run rough 97.6724 0.03 2.3 good 25 94.97 24 0.03 5 good  0 90.97 24 0.03 9 good 3385.97 24 0.03 14 good 33

Another experiment was run in which HC-1 was applied to the 5-milMelinex 618 film with a metered, precision die coating process. Thehardcoat formulation with HC-1 and Des N100/0.85 PET3A/0.15 HFPO(Preparation 5.2) was diluted to 30 wt-% solids in isopropanol andcoated onto the 5-mil PET backing to achieve a dry thickness of 5microns. A flow meter was used to monitor and set the flow rate of thematerial from a pressurized container. The flow rate was adjusted bychanging the air pressure inside the sealed container which forcesliquid out through a tube, through a filter, the flow meter and thenthrough the die. The dried and cured film was wound on a take up roll.

The coatings were dried in a 10-foot oven at 100 degrees Celsius, andcured with a 300-watt Fusion Systems H bulb at 100, 75, 50, and 25%power. The coating shown in Table 12 below was evaluated in a series oftests. The sand test was run for 15 minutes at 300 rpm. The Steel WoolTest was run checking for damage to the coating at 100, 250, 500, 750,and 1000 cycles. The results are summarized in Table 12. Contact angleswere also run on selected samples before and after testing and theseresults are shown in Table 13.

TABLE 12 Taber testing (Preparation Steel Wool Taber Change in haze Wt.% Number 5.2) (Cycles testing % from initial HC-1 in Weight % in UVdoseInk without haze after value in % after coating coating % powerrepellency scratches) 500 cycles 500 cycles 99.27 0.73 100 0 1000 10.8310.51 99.27 0.73 75 0 1000 8.38 8.04 99.27 0.73 50 0 1000 11.05 10.6299.27 0.73 25 0 1000 8.35 8.04

Selected coatings from Table 12 were tested for contact angles withwater and hexadecane, and are identified by the UV dose % power used incuring the coatings. The results are summarized in Table 13:

TABLE 13 After 1000 Initial After Sand cycles - Steel Advancing/ TestingWool Liquid used Static/ Advancing/ Advancing/ to test Receding Static/Static/ UV dose contact Contact Receding Receding % power angle anglesContact angles Contact angles 100 Water 110/123/98 94/111/68 107/119/89100 Hexadecane —/72/64 —/61/49 —/69/62 25 Water 107/120/84 91/105/53103/118/72 25 Hexadecane —/71/62 —/56/40 —/63/55Preparation of Hardcoat Substrate S1

A primed 5 mil transparent polyethylene terephthalate (PET) film wasobtained from E.I. duPont de Nemours and Company, Wilmington, Del. underthe trade designation “Melinex 618”. A hardcoat compositionsubstantially the same as Example 3 of U.S. Pat. No. 6,299,799 (HC-1)was coated onto the primed surface with a metered, precision die coatingprocess. The hardcoat was diluted in IPA to 30 wt-% solids and coatedonto the 5-mil PET backing to achieve a dry thickness of 5 microns. Aflow meter was used to monitor and set the flow rate of the materialfrom a pressurized container. The flow rate was adjusted by changing theair pressure inside the sealed container which forces liquid out througha tube, through a filter, the flow meter and then through the die. Thedried and cured film was wound on a take up roll and used as the inputbacking Hardcoat Substrate S-1 for the coating solutions describedbelow.

The hardcoat coating and drying parameters were as follows:

Coating width: 6″ (15 cm) Web Speed: 30 feet (9.1 m) per minute Solution% Solids: 30.2% Filter: 2.5 micron absolute Pressure Pot: 1.5 galloncapacity (5.7 1) Flow rate: 35 g/min Wet Coating Thickness: 24.9 micronsDry Coating Thickness: 4.9 microns Conventional Oven Temps: Zone 1 -140° F. (60° C.) Zone 2 - 160° F. (53° C.) Zone 3 - 180° F. (82° C.)Each zone was 10 ft (3 m) in length.

The coating compositions described in Table 14 were coated onto thehardcoat layer S1 using a precision, metered die coater. For this step,a syringe pump was used to meter the solution into the die. Thesolutions were diluted with MEK to a concentration of 1% and coated ontothe hardcoat layer to achieve a dry thickness of 60 nm. The material wasdried in a conventional air flotation oven and then cured a 600 wattFusion Systems bulb under nitrogen using the conditions show below:

Coating width: 4″ (10 cm) Web Speed: 20 feet per minute Solution %Solids: 1.0% Pump: 60 cc Syringe Pump Flow rate: 1.2 cc/min Wet CoatingThickness: 4.1 microns Dry Coating Thickness: 60 nm Conventional OvenTemps: Zone 1 - 65° C. Zone 2 - 65° C. Both zones at 10 ft (3 m) inlength.

The coatings were made and tested for ink repellency before and after asand test at 300 rpm for 15 min and for initial water static contactangle.

TABLE 14 HFPO- Static water Urethane HFPO- % Ink Contact TMPTAPreparation- AEA Darocur Repellency angle (range in (%) 6 (%) (31a) 1173loss degrees) 95 3.75 1.25 4 0 100-101 90 7.5 2.5 4 0 85 11.25 3.75 4 0110-111 80 15 5 4 0 90 10 4 0 93-94 80 20 4 0 103-104Compatibility Evaluation of HFPO-Monoacrylates with HydrocarbonMulti-Functional Acrylates and Mixtures of Hydrocarbon Multi-FunctionalAcrylates with Perfluoropolyether Urethane Multiacrylates

MEK solutions of the mixtures shown in Table 15 were prepared at 30%solids. After thoroughly mixing the desired components at the ratiosshown, approximately 3 ml of each soln was deposited onto a glassmicroscope slide and the solvent was allowed to evaporate over 16 hrs.The compatibility of the mixtures were than noted as either incompatibleor compatible. An “Incompatible” observation was noted when the dried,uncured 100% solids mixture was either hazy or showed clear phaseseparations such as “oil-water type” phase separation behavior.Compatible mixtures were observed to be clear or transparent with novisible detection of a second phase in the mixture. The mixtures werefurther diluted to 1.25% solids with MEK and 4% Darocur 1173photoinitiator based on the solid content of the solution was added tothe mixtures. An approximate 40 nm coating of each of these solutionswas prepared on the substrate Si by the use of a #2.5 Meyer Rod. Thecoatings were allowed to dry at room temperature and were cured at 10fpm, 2-passes by use of Fusion Systems UV processor Model LCS BQ, The UVsystem was equipped with a Fusion Systems 500 w Light-Hammer model LH6PS and used a H Bulb as the UV source. The cure chamber was flushedcontinuously with a positive nitrogen flow of approximately 20 psi.Contact angles were measured as described elsewhere in this application.

TABLE 15 Formulations used in Compatibility Studies of HFPO-urethanes,Non-urethane HFPO-monoacrylates and Hydrocarbon MultifunctionalAcrylates. wt % Static Water HFPO Contact Compatibility wt % UrethaneHFPO Type of Angle at 100% Sample TMPTA Acrylate Acrylate Acrylate wt %F 40 nm Solids 15-1 97 0 3 31a 1.85 104 incompatible 15-2 97 0 3 31b1.74 96 incompatible 15-3 97 0 3 31c 1.72 101 incompatible 15-4 97 0 331d 1.81 102 incompatible 15-5 90 0 10 31a 6.17 103 incompatible 15-6 900 10 31b 5.8 102 incompatible 15-7 90 0 10 31c 5.73 99 incompatible 15-890 0 10 31d 6.02 101 incompatible 15-9 87 10 3 31a 3.41 101 compatible15-10 87 10 3 31b 3.3 100 compatible 15-11 87 10 3 31c 3.28 98compatible 15-12 87 10 3 31d 3.37 102 compatible 15-13 85 10 5 31a 4.65106 compatible 15-14 85 10 5 31b 4.46 101 compatible 15-15 85 10 5 31c4.42 101 compatible 15-16 85 10 5 31d 4.57 104 compatible 15-17 97 3 0None 0.47 65 compatible 15-18 90 10 0 None 1.56 94 compatible 15-19 8020 0 None 3.12 104 compatibleCompatibility Studies of Perfluoropolyether Urethane Multiacrylates withPerfluoropolyether (PFPE) Multiacrylates, Hydrocarbon Multi-FunctionalAcrylates and Nonurethane PFPE Multiacrylates

MEK solutions of the mixtures shown in Table 16 were prepared at 30%solids. After mixing the desired components thoroughly, approximately 3ml of each soln was deposited onto a glass microscope slide and thesolvent was allowed to evaporate. After 16 hrs, the compatibility of themixtures was noted according to the criteria described for Table 15.

TABLE 16 PFPE HFPO-Urethane multiacrylates Calc wt % F Sample SR 351 #6at 3 wt % in Coating Compatibility 16-1 87 10 HFPO Prep 25 3.32compatible 16-2 87 10 HFPO Prep 28 3.31 compatible 16-3 87 10 HFPO Prep29 3.06 compatible 16-4 87 10 LTM Diacrylate 3.36 compatible 16-5 87 10CN 4000 3.21 compatible 16-6 97 0 HFPO Prep 25 1.76 incompatible 16-7 970 HFPO Prep 28 1.75 incompatible 16-8 97 0 HFPO Prep 29 1.50incompatible 16-9 97 0 LTM Diacrylate 1.80 incompatible  16-10 97 0 CN4000 1.65 incompatible Each formulation also contained 4 wt % Darocur1173 photoinitiator

Formulations described in Table 16, were coated on S-1 at approximately40 nm coating weight using the same method as described in Table 15.Contact angle measurements and durability were determined as previouslydescribed. The results are shown in Table 17.

TABLE 17 Test Results of Formulations of Table 16 Static Water ContactDurability Angle Sand test 300 rpms/ Before Durability Sample PFPEDescription 15 min/50 g sand Testing 16-1 HFPO Prep 25 Yes 108.3 16-2HFPO Prep 28 Yes 105.4 16-3 HFPO Prep 29 Yes 105.6 16-4 LTM DiacrylateYes 105.7 16-5 CN 4000 Yes 106.2 16-6 HFPO Prep 25 Yes-partial 83.6 16-7HFPO Prep 28 No 97.4 16-8 HFPO Prep 29 No 77 16-9 LTM Diacrylate No 70.6 16-10 CN 4000 No 98.2

Coating formulations comprising the multifunctional PFPE acrylates(Preps 25, 28, 29), LTM diacrylate, and CN4000, were prepared atconstant weight percent fluorine by mixing with TMPTA. Thesecompositions were compared to Coating Formulation #9 of Table 15, toexemplify the utility of the HFPO—U acrylate as a compatibilizer foreither PFPE Multifunctional acrylate or HFPO-monoacrylates. Thecompositions are shown in Table 18 and the surface contact angles anddurabilities are shown in Table 19.

TABLE 18 Formulations for Perfluoropolymer Polyethers MultifunctionalAcrylates without HFPO-Urethane Formulated to Similar wt-% Fluorine wt %Type of Coating Sample TMPTA PFPE PFPE Darocur wt % F Quality 18-1 93.56.5 HFPO Prep 4 3.80 Poor- 25 dewets/ streaks 18-2 94 6 HFPO Prep 4 3.47Good 28 18-3 93.2 6.8 HFPO Prep 4 3.40 Good 29 18-4 94.2 5.8 LTM 4 3.47Poor- Diacrylate dewets/ streaks 18-5 93.7 6.3 CN 4000 4 3.47 Good 16-93.41 Good

TABLE 19 40 nm Coatings of Formulations of Table 18 (coated as describedfor Table 15) 1.25% solids, Ink repellency ~40 nm IR loss after sandtest thickness Water Coating quality 300 rpms/15 min/50 g Sample Static40 nm sand 18-1 108.9 Good 80% 18-2 101.6 Good 80% 18-3 95.8 Good 100%18-4 98.6 Good 35% 18-5 100.1 Good 41% 16-9 108.7 Good 0%

While the invention has been described in terms of preferredembodiments, it will be understood, of course, that the invention is notlimited thereto since modifications may be made by those skilled in theart, particularly in light of the foregoing teachings.

What is claimed is:
 1. A fluorocarbon- andurethane-(meth)acryl-containing composition comprising aperfluoropolyether urethane having a perflurorpolyether moiety and amulti-meth(acryl) group having the chemical formula:(R_(i))_(c)—(NHC(O)OQ(A)_(p))_(n),—(NHC(O)XQ-R_(f2)(QXC(O)NH)_(u))_(r)—,—(NHC(O)OQ(A)_(t)Q₁Q(A)_(t)OC(O)NH)_(v)—wherein R_(i) is a residue of a multi-isocyanate; c is 1 to 50; X is O,S or NR, where R is H or an alkyl group comprising 1 to 4 carbon atoms;Q and Q₁ are each independently a connecting group of valency at least2; A is a (meth)acryl functional group having the formula(—XC(O)C(R₂)═CH₂), wherein R₂ is an alkyl group having 1 to 4 carbonatoms or H or F; R_(f2) is a multi-valent perfluoropolyether moietyhaving the formula Y((R_(fc1)O)_(x)C_(d1)F_(2d1))_(b), wherein eachR_(fc1) is independently selected from: —CF(CF₃)CF₂—, —CF₂CF₂CF₂—, and(CH₂C(CH₃)(CH₂OCH₂CF₃)CH₂—)_(aa) where aa is 2 or greater; each x isindependently an integer greater than or equal to 2, d1 is an integerfrom 0 to 6; Y represents a polyvalent organic group or covalent bondhaving a valence of b, and b represents an integer greater than or equalto 2; p is 2 to 6; u is 1 to 3; t is 1-6; r is at least 1; and n or v isat least
 1. 2. The fluorocarbon- and urethane-(meth)acryl-containingcomposition of claim 1 wherein the perfluoropolyether urethane comprises_(n)(_(p)(A)QO(O)CHN)—R_(i)—(NHC(O)XQ-R_(f2)(QXC(O)NH)_(u))_(r),or_(v)(HN(O)CO(A)_(t)QQ₁(A)_(t)QO(O)CHN)—R_(i)—(NHC(O)XQ-R_(f2)(QXC(O)NH)_(u))_(r).3. A fluorocarbon- and urethane-(meth)acryl-containing compositioncomprising a perfluoropolyether urethane having a perflurorpolyethermoiety and a multi-meth(acryl) group having the chemical formula:(R_(i))_(c)—(NHC(O)XQR_(f))_(m),—(NHC(O)OQ(A)_(p))_(n),R_(f)(Q)(XC(O)NH)_(y))_(z)—,—(NHC(O)OQ(A)_(t)Q₁(A)_(t)OC(O)NH)_(v)— wherein R_(i) is a residue of amulti-isocyanate; c is 1 to 50; X is O, S or NR, where R is H or analkyl group comprising 1 to 4 carbon atoms; R_(f) is a monovalentperfluoropolyether moiety comprising groups of the formulaF(R_(fc)O)_(x)C_(d)F_(2d), wherein each R_(fc) independently representsa fluorinated alkylene group having from 1 to 6 carbon atoms, each x isan integer greater than or equal to 2, and d is an integer from 1 to 6;Q and Q₁ are each independently a connecting group of valency at least2; A is a (meth)acryl functional group having the formula(—XC(O)C(R₂)═CH₂), wherein R₂ is an alkyl group having 1 to 4 carbonatoms or H or F; p is 2 to 6; y is independently 2 or greater; t is 1-6;m or z is at least 1; n or v is at least 1; and at least one of v or zis
 1. 4. The composition of claim 1 with the proviso that when X is O, Qis not methylene.
 5. The composition of claim 1 wherein X is S or NR. 6.The composition of claim 1 wherein Q is an alkylene having at least twocarbon atoms.
 7. The composition of claim 1 wherein Q is a straightchain, branched chain, or cycle-containing connecting group.
 8. Thecomposition of claim 7 wherein Q is selected from the group consistingof a covalent bond; an arylene; an aralkylene; and alkarylene.
 9. Thecomposition of claim 7 wherein Q comprises a heteroatom selected from O,N, and S.
 10. The composition of claim 7 wherein Q comprises aheteroatom-containing functional group selected from carbonyl andsulfonyl.
 11. The composition of claim 7 wherein Q is a straight chainalkylene group comprising heteroatoms selected from O, N, S; aheteroatom-containing functional group selected from carbonyl andsulfonyl, and combinations thereof.
 12. The composition of claim 7wherein Q is branched chain or cycle-containing alkylene group.
 13. Thecomposition of claim 1 wherein Q is a nitrogen containing group.
 14. Thecomposition of claim 13 wherein Q contains an amide group.
 15. Thecomposition of claim 1 wherein the composition further comprisesethylene oxide repeat units.
 16. The composition of claim 1 wherein n is2.